Luminescence device and display apparatus

ABSTRACT

A metal coordination compound having a structure according to formula (1) or (3), wherein ligand L is a phenylisoquinoline ligand and ligand L2 is different from L:  
                 
A luminescence device and a display apparatus using this metal coordination compound are provided.

This application is a division of Ser. No. 11/329,181, filed Jan. 11,2006, which is a division of application Ser. No. 10/073,012, filed Feb.12, 2002, now U.S. Pat. No. 7,147,935, which is a continuation of 5International Application PCT/JP01/10487, filed Nov. 30, 2001. All priorapplications are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to an organic luminescence device (alsocalled an organic electroluminescence device or organic EL device) foruse in a planar light source, a planar display, etc. Particularly, thepresent invention relates to a novel metal coordination compound and aluminescence device having a high luminescence efficiency and causinglittle change with time by using a metal coordination compound of aspecific structure.

BACKGROUND ART

An old example of organic luminescence device is, e.g., one usingluminescence of a vacuum-deposited anthracene film (Thin Solid Films, 94(1982) 171). In recent years, however. in view of advantages, such aseasiness of providing a large-area device compared with an inorganicluminescence device, and possibility of realizing desired luminescencecolors by development of various new materials and drivability at lowvoltages, an extensive study thereon for device formation as aluminescence device of a high-speed responsiveness and a highefficiency, has been conducted.

As precisely described in Macromol. Symp. 125, 1-48 (1997), for example,an organic EL device generally has an organization comprising a pair ofupper and lower electrodes formed on a transparent substrate, andorganic material layers including a luminescence layer disposed betweenthe electrodes.

In the luminescence layer, aluminum quinolinol complexes (inclusive ofAlq3 shown hereinafter as a representative example) having anelectron-transporting characteristic and a luminescence characteristic,are used for example. In a hole-transporting layer, a material having anelectron-donative property, such as a triphenyldiamine derivative(inclusive of α-NPD shown hereinafter as a representative example), isused for example.

Such a device shows a current-rectifying characteristic such that whenan electric field is applied between the electrodes, holes are injectedfrom the anode and electrons are injected from the cathode.

The injected holes and electrons are recombined in the luminescencelayer to form excitons, which emit luminescence when they aretransitioned to the ground state.

In this process, the excited states include a singlet state and atriplet state and a transition from the former to the ground state iscalled fluorescence and a transition from the latter is calledphosphorescence. Materials in theses states are called singlet excitonsand triplet excitons, respectively.

In most of the organic luminescence devices studied heretofore,fluorescence caused by the transition of a singlet exciton to the groundstate, has been utilized. On the other hand, in recent years, devicesutilizing phosphorescence via triplet excitons have been studied.

Representative published literature may include:

Article 1: Improved energy transfer in electrophosphorescent device (D.F. O'Brien, et al., Applied Physics Letters, Vol. 74, No. 3, p. 422(1999)); and

Article 2: Very high-efficiency green organic light-emitting devicesbased on electrophosphorescence (M. A. Baldo, et al., Applied PhysicsLetters, Vol. 75, No. 1, p. 4 (1999)).

In these articles, a structure including four organic layers sandwichedbetween the electrodes, and the materials used therein includecarrier-transporting materials and phosphorescent materials, of whichthe names and structures are shown below together with theirabbreviations.

Alq3: aluminum quinolinol complex

α-NPD: N4,N4′-di-naphthalene-1-yl-N4,N4′-diphenyl-biphenyl-4,4′-diamine

CBP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline

PtOEP: platinum-octaethylporphyrin complex

Ir(ppy)₃: iridium-phenylpyridine complex

The above-mentioned Articles 1 and 2 both have reported structures, asexhibiting a high efficiency, including a hole-transporting layercomprising α-NPD, an electron-transporting layer comprising Alq3, anexciton diffusion-preventing layer comprising BCP, and a luminescencelayer comprising CBP as a host and ca 6% of PtOEP or Ir(ppy)₃ as aphosphorescent material dispersed in mixture therein.

Such a phosphorescent material is particularly noted at present becauseit is expected to provide a high luminescence efficiency in principlefor the following reasons. More specifically, excitons formed by carrierrecombination comprise singlet excitons and triplet excitons in aprobability ratio of 1:3. Conventional organic EL devices have utilizedfluorescence of which the luminescence efficiency is limited to at most25%. On the other hand, if phosphorescence generated from tripletexcitons is utilized, an efficiency of at least three times is expected,and even an efficiency of 100%, i.e., four times, can be expected inprinciple, if a transition owing to intersystem crossing from a singletstate having a higher energy to a triplet state is taken into account.

However, like a fluorescent-type device, such an organic luminescencedevice utilizing phosphorescence is generally required to be furtherimproved regarding the deterioration of luminescence efficiency anddevice stability.

The reason of the deterioration has not been fully clarified, but thepresent inventors consider as follows based on the mechanism ofphosphorescence.

In the case where the luminescence layer comprises a host materialhaving a carrier-transporting function and a phosphorescent guestmaterial, a process of phosphorescence via triplet excitons may includeunit processes as follows:

1. transportation of electrons and holes within a luminescence layer,

2. formation of host excitons,

3. excitation energy transfer between host molecules,

4. excitation energy transfer from the host to the guest,

5. formation of guest triplet excitons, and

6. transition of the guest triplet excitons to the ground state andphosphorescence.

Desirable energy transfer in each unit process and luminescence arecaused in competition with various energy deactivation processes.

Needless to say, a luminescence efficiency of an organic luminescencedevice is increased by increasing the luminescence quantum yield of aluminescence center material.

Particularly, in a phosphorescent material, this may be attributable toa life of the triplet excitons which is longer by three or more digitsthan the life of a singlet exciton. More specifically, because it isheld in a high-energy excited state for a longer period, it is liable toreact with surrounding materials and cause polymer formation among theexcitons, thus incurring a higher probability of deactivation processresulting in a material change or life deterioration.

Further, in view of the formation of a full-color display device,luminescence materials providing luminescence colors which are as closeas possible to pure three primary colors of blue, green and red, aredesired, but there have been few luminescence materials giving aluminescence color of pure red, so that the realization of a goodfull-color display device has been restricted.

DISCLOSURE OF INVENTION

Accordingly, a principal object of the present invention is to provide acompound capable of high efficiency luminescence and showing a highstability as a luminescent material for use in a phosphorescentluminescence device. Particularly, it is an object to provide aluminescence material compound which is less liable to cause energydeactivation in a long life of excited energy state and is alsochemically stable, thus providing a longer device life. A further objectof the present invention is to provide a red luminescence materialcompound capable of emitting pure red suitable for forming a full-colordisplay device.

Inclusively, principal objects of the present invention are to provide aluminescence material which exhibits a high luminescence efficiency,retains a high luminance for a long period and is capable of redluminescence based on phosphorescent luminescence materials, and alsoprovide a luminescence device and a display apparatus using the same.

In the present invention, a metal complex is used as a luminescencematerial, particularly a novel luminescent metal complex compoundcomprising iridium as a center metal and an isoquinolyl group as aligand.

More specifically, the present invention uses as a luminescence materiala metal coordination compound having at least one partial structurerepresented by formula (1) below:ML  (1),wherein the partial structure ML is represented by formula (2) below:

wherein M is a metal atom of Ir, Pt, Rh or Pd; N and C are nitrogen andcarbon atoms, respectively; A is a cyclic group capable of having asubstituent, including the carbon atom and bonded to the metal atom Mvia the carbon atom; B is an isoquinolyl group capable of having asubstituent, including the nitrogen atom and bonded to the metal atom Mvia the nitrogen atom, with the proviso that one or two of CH groupsforming the isoquinolyl group can be replaced with a nitrogen atom andthe cyclic group A is coordination-bonded to a position-1 carbon atom ofthe isoquinolyl group.

More specifically, the present invention uses a metal coordinationcompound having an entire structure represented by formula (3) below:ML_(m)L′_(n)  (3),wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutuallydifferent bidentate ligands; m is 1, 2 or 3, and n is 0, 1 or 2 with theproviso that m+n is 2 or 3; a partial structure ML′_(n) is representedby formula (4), (5) or (6) shown below:

The present invention also uses as a luminescence material, a metalcoordination compound which is entirely represented by formula (7)below:

wherein Cl denotes a chlorine atom, M′ denotes iridium Ir or rhodium Rh,and m′ is 2.

The present invention also provides high-performance organicluminescence device and display apparatus using the above-mentionednovel metal coordination compound as an organic luminescence material.

Preferred embodiments of the present invention include the following:

A metal coordination compound, wherein n is 0 in the above formula (3).

A metal coordination compound, wherein the cyclic groups A and A′ areindependently selected from phenyl group, naphthyl group, thienyl group,fluorenyl group, thianaphthyl group, acenaphthyl group, anthranyl group,phenanthrenyl group, pyrenyl group, or carbazolyl group, as an aromaticcyclic group capable of having a substituent with the proviso that thearomatic cyclic group can include one or two CH groups that can bereplaced with a nitrogen atom.

A metal coordination compound, wherein the cyclic groups A and A′ areselected from phenyl group, 2-naphthyl group, 2-thienyl group,2-fluorenyl group, 2-thianaphthyl group, 2-anthranyl group,2-phenanthrenyl group, 2-pyrenyl group, or 3-carbazolyl group, as anaromatic cyclic group capable of having a substituent with the provisothat the aromatic cyclic group can include one or two CH groups that canbe replaced with a nitrogen atom.

A metal coordination compound, wherein the aromatic cyclic group isphenyl group capable of having a substituent.

A metal coordination compound, wherein a hydrogen atom is attached to aposition-6 carbon atom of the phenyl group capable of having asubstituent next to a position-1 carbon atom bonded to the cyclic groupB.

A metal coordination compound, wherein the cyclic groups B′ and B″ areindependently selected from isoquinolyl group, quinolyl group,2-azaanthranyl group, phenanthridinyl group, pyridyl group, oxazolylgroup, thiazolyl group, benzoxazolyl group, or benzthiazolyl group, asan aromatic cyclic group capable of having a substituent with theproviso that the aromatic cyclic group can include one or two CH groupsthat can be replaced with a nitrogen atom.

A metal coordination compound, wherein the cyclic groups B′ and B″ areselected from isoquinolyl group or pyridyl group, as an aromatic cyclicgroup capable of having a substituent with the proviso that the aromaticcyclic group can include one or two CH groups that can be replaced witha nitrogen atom.

A metal coordination compound, wherein the cyclic group B′ in theformula (4) is isoquinolyl group capable of having a substituent.

A metal coordination compound, wherein the cyclic groups A, A′, B, B′and B″ are independently non-substituted, or have a substituent selectedfrom a halogen atom or a linear or branched alkyl group having 1 to 20carbon atoms {of which the alkyl group can include one ornon-neighboring two or more methylene groups that can be replaced with—O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—, —C≡C—, or a divalent aromaticgroup capable of having a substituent (that is a halogen atom, or alinear or branched alkyl group having 1 to 20 carbon atoms (of which thealkyl group can include one or non-neighboring two or more methylenegroups that can be replaced with —O—, and the alkyl group can include ahydrogen atom that can be optionally replaced with a fluorine atom)),and the alkyl group can include a hydrogen atom that can be optionallyreplaced with a fluorine atom}.

A metal coordination compound, wherein the cyclic group A in the formula(7) is selected from phenyl group, naphthyl group, thienyl group,fluorenyl group, thianaphthyl group, acenaphthyl group, anthranyl group,phenanthrenyl group, pyrenyl group, or carbazolyl group, as an aromaticcyclic group capable of having a substituent with the proviso that thearomatic cyclic group can include one or two CH groups that can bereplaced with a nitrogen atom.

A metal coordination compound, wherein the aromatic cyclic group isselected from phenyl group, 2-naphthyl group, 2-thienyl group,2-fluorenyl group, 2-thianaphthyl group, 2-anthranyl group,2-phenanthrenyl group, 2-pyrenyl group or 3-carbazolyl group, eachcapable of having a substituent with the proviso that the aromaticcyclic group can include one or two CH groups that can be replaced witha nitrogen atom.

A metal coordination compound, wherein the aromatic cyclic group isphenyl group capable of having a substituent.

A metal coordination compound, wherein a hydrogen atom is attached to aposition-6 carbon atom of the phenyl group capable of having asubstituent next to a position-1 carbon atom bonded to the cyclic groupB.

A metal coordination compound, wherein the cyclic groups A and B in theformula (7) are independently non-substituted, or have a substituentselected from a halogen atom or a linear or branched alkyl group having1 to 20 carbon atoms {of which the alkyl group can include one ornon-neighboring two or more methylene groups that can be replaced with—O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—, —C≡C—, or a divalent aromaticgroup capable of having a substituent (that is a halogen atom, a cyanoatom, a nitro atom, a trialkylsilyl group (of which the alkyl groups areindependently a linear or branched alkyl group), a linear or branchedalkyl group having 1 to 20 carbon atoms (of which the alkyl group caninclude one or non-neighboring two or more methylene groups that can bereplaced with —O—, and the alkyl group can include a hydrogen atom thatcan be optionally replaced with a fluorine atom)), and the alkyl groupcan include a hydrogen atom that can be optionally replaced with afluorine atom}.

A metal coordination compound, wherein M in the formula (1) is iridium.

A metal coordination compound, wherein M in the formula (7) is iridium.

A metal coordination compound, having a partial structure ML representedby the formula (2) and represented by formula (8) below:Ir[Rp-Ph-IsoQ-R′q]₃  (8),wherein Ir is iridium; partial structure Ph-IsoQ denotes1-phenylisoquinolyl group; substituents R and R′ are selected fromhydrogen, fluorine or a linear or branched alkyl group represented byC_(n)H_(2n+1) (wherein H can be replaced with F, a non-adjacentmethylene group can be replaced with oxygen and n is an integer of 1 to20), p and q are integers of at least 1 representing numbers of thesubstituents R and R′ bonded to the phenyl group and the isoguinolylgroup, respectively, wherein a position-2 carbon atom of the phenylgroup and a nitrogen atom of IsoQ are coordination-bonded to Ir.

A metal coordination compound, wherein the partial structure Rp-Ph is4-alkylphenyl group in the formula (8), and the substituent R′ ishydrogen.

A metal coordination compound, wherein in the formula (8), thesubstituent R is hydrogen, and R′q represents a fluoro ortrifluoromethyl group substituted at a 4- or 5-position.

A metal coordination compound, wherein in the formula (8), the partialstructure Rp-Ph- is 5-fluorophenyl group, and R′q is a hydrogen atom ora fluorine atom or trifluoromethyl group substituted at a 4- or5-position.

A metal coordination compound, wherein in the formula (8), the partialstructure Rp-Ph- is 4-fluorophenyl group, and R′q is a hydrogen atom ora fluorine atom or trifluoromethyl group substituted at a 4- or5-position.

A metal coordination compound, wherein in the formula (8), the partialstructure Rp-Ph- is 3,5-difluorophenyl group, and R′q is a hydrogen atomor fluorine atom or trifluoromethyl group substituted at a 4- or5-position.

A metal coordination compound, wherein in the formula (8), the partialstructure Rp-Ph- is 3,4,5-trifluorophenyl group, and R′q is a hydrogenatom or a fluorine atom or trifluoromethyl group substituted at a 4- or5-position.

A metal coordination compound, wherein in the formula (8), the partialstructure Rp-Ph- is 4-trifluoromethylphenyl group, and R′q is a hydrogenatom or a fluorine atom or trifluoromethyl group substituted at a 4- or5-position.

A metal coordination compound, wherein in the formula (8), the partialstructure Rp-Ph- is 5-trifluoromethylphenyl group, and R′q is a hydrogenatom or a fluorine atom or trifluoromethyl group substituted at a 4- or5-position.

A metal coordination compound, wherein in the formula (8), the structureRp-Ph is a 1-(3,4,5,6-tetrafluorophenyl) group, and in R′q, q is 1 or 6and R′ is a hydrogen atom, a trifluoromethyl group substituted at a 4-or 5-position or such that IsoQ-R′q is a3,4,5,6,7,8-hexafluoroisoquinoline group.

A metal coordination compound, wherein in the formula (8), the partialstructure Rp-Ph- is 4-alkylphenyl group (wherein the alkyl group is alinear or branched alkyl group having 1 to 6 carbon atoms), and R′q ishydrogen.

A metal coordination compound, wherein in the formula (8), the partialstructure Rp-Ph- is 4-alkoxyphenyl group (wherein the alkoxy group is alinear or branched alkoxy group having 1 to 6 carbon atoms), and R′q ishydrogen.

A metal coordination compound, wherein in the formala (8), the partialstructure Rp-Ph- is a 4-trifluoro-methyloxyphenyl group, and R′q is ahydrogen or fluoro group or trifluoromethyl group substituted at a 4- or5-position.

A metal coordination compound, which is represented by the formula (3)and is also represented by formula (9) below:IrL_(m)L′_(n)  (9)wherein Ir represents iridium.

A metal coordination compound, represented by the formula (9), whereinL_(m) is represented by a formula of [4-alkylphenylisoquinoline]₂(wherein the alkyl group is represented by C_(n)H_(2n+1) and n is aninteger of 1 to 8), and L′_(n) is 1-phenylisoquinoline.

A metal coordination compound, represented by the formula (9), whereinL_(m) is represented by a formula [1-phenylisoquinoline]₂, and L′_(n) is4-alkylphenylisoquinoline (wherein the alkyl group has 1 to 8 carbonatoms).

A metal coordination compound, wherein one or two CH groups in theisoquinolyl group capable of having a substituent in the formula (1) arereplaced with a nitrogen atom.

A metal coordination compound, wherein one or two CH groups in theisoquinolyl group capable of having a substituent in the formula (7) arereplaced with a nitrogen atom.

An organic luminescence device, comprising: a pair of electrodesdisposed on a substrate, and a luminescence unit comprising at least oneorganic compound disposed between the electrodes, wherein the organiccompound comprises a metal coordination compound having at least onepartial structure represented by the formula (1) in claim 1.

An organic luminescence device, wherein the organic compound comprises ametal coordination compound having a structure represented by theformula (3).

An organic luminescence device, wherein the organic compound comprises ametal coordination compound having a structure represented by theformula (8).

An organic luminescence device wherein the organic compound comprises ametal coordination compound having a structure represented by theformula (9).

An organic luminescence device, wherein a voltage is applied between theelectrodes to emit phosphorescence.

An organic luminescence device, wherein the phosphorescence is red inluminescence color.

A picture display apparatus, comprising the above-mentioned organicluminescence device, and a means for supplying electric signals to theorganic luminescence device.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates embodiments of the luminescence device according tothe present invention.

FIG. 2 illustrates a simple matrix-type organic EL device according toExample 8.

FIG. 3 illustrates drive signals used in Example 8.

FIG. 4 schematically illustrates a panel structure including an ELdevice and drive means.

FIG. 5 is a graph showing voltage-efficiency luminance characteristicsof a device of Example 27.

FIG. 6 is a graph showing external Quantum efficiency of a device ofExample 27.

FIG. 7 shows a ¹H-NMR spectrum of a solution in heavy chloroform of1-phenylisoquinoline.

FIG. 8 shows a ¹H-NMR spectrum of a solution in heavy chloroform oftris(1-phenyl-isoquinoline-C²,N)iridium (III).

FIG. 9 shows a ¹H-NMR spectrum of a solution in heavy chloroform of1-(4-methylphenyl)-isoquinoline.

FIG. 10 shows a ¹H-NMR spectrum of a solution in heavy chloroform oftetrakis[1-4-methylphenyl)isoquinoline-C²,N](μ-dichloro)-diiridium(III).

FIG. 11 shows a ¹H-NMR spectrum of a solution in heavy chloroform ofbis[1-(4-methylphenyl)isoquinoline-C²,N](acetylacetonato)-iridium (III).

FIG. 12 shows a ¹H-NMR spectrum of a solution in heavy chloroform oftris[1-(4-methylphenyl)isoquinoline-C²,N]iridium (III).

FIG. 13 shows a ¹H-NMR spectrum of a solution in heavy chloroform ofbis[1-(4-n-octylphenyl)isoquinoline-C²,N](acetylacetonato)-iridium(III).

BEST MODE FOR PRACTICING THE INVENTION

Basic structures of organic EL devices formed according to the presentinvention are illustrated in FIG. 1(a), (b) and (c).

As shown in FIG. 1, an organic luminescence device generally comprises,on a transparent electrode 15, a 50 to 200 nm-thick transparentelectrode 14, a plurality of organic film layers and a metal electrode11 formed so as to sandwich the organic layers.

FIG. 1(a) shows an embodiment wherein the organic luminescence devicecomprises a luminescence layer 12 and a hole-transporting layer 13. Thetransparent electrode 14 may comprise ITO, etc., having a large workfunction so as to facilitate hole injection from the transparentelectrode 14 to the hole-transporting layer 13. The metal electrode 11comprises a metal material having a small work function, such asaluminum, magnesium or alloys of these elements, so as to facilitateelectron injection into the organic luminescence device.

The luminescence layer 12 comprises a compound according to the presentinvention. The hole-transporting layer 13 may comprise, e.g., atriphenyldiamine derivative, as represented by α-NPD mentioned above,and also a material having an electron-donative property as desired.

A device organized above exhibits a current-rectifying characteristic,and when an electric field is applied between the metal electrode 11 asa cathode and the transparent electrode 14 as an anode, electrons areinjected from the metal electrode 11 into the luminescence layer 12, andholes are injected from the transparent electrode 15. The injected holesand electrons are recombined in the luminescence layer 12 to formexcitons, which cause luminescence. In this instance, thehole-transporting layer 13 functions as an electron-blocking layer toincrease the recombination efficiency at the boundary between theluminescence layer 12 and the hole-transporting layer 13, therebyproviding an enhanced luminescence efficiency.

Further, in the structure of FIG. 1(b), an electron-transporting layer16 is disposed between the metal electrode 11 and the luminescence layer12 in FIG. 1(a). As a result, the luminescence function is separatedfrom the functions of electron transportation and hole transportation toprovide a structure exhibiting more effective carrier blocking, thusincreasing the luminescence efficiency. The electron-transporting layer16, may comprise, e.g., an oxadiazole derivative.

FIG. 1(c) shows another desirable form of a four-layer structure,including a hole-transporting layer 13, a luminescence layer 12, anexciton diffusion prevention layer 17 and an electron-transporting layer16, successively from the side of the transparent electrode 14 as theanode.

The luminescence materials used in the present invention are mostsuitably metal coordination compounds represented by the above-mentionedformulae (1) to (9), which are found to cause high-efficiencyluminescence in a red region around 600 mm, retain high luminance for along period and show little deterioration by current passage.

The metal coordination compound used in the present invention emitsphosphorescence, and its lowest excited state is believed to be an MLCT*(metal-to-ligand charge transfer) excited state or ππ* excited state ina triplet state, and phosphorescence is caused at the time of transitionfrom such a state to the ground state.

<<Measurement Methods>>

Hereinbelow, methods for measurement of some properties and physicalvalues described herein for characterizing the luminescence material ofthe present invention will be described.

(1) Judgment between phosphorescence and fluorescence

The identification of phosphorescence was effected depending on whetherdeactivation with oxygen was caused or not. A solution of a samplecompound in chloroform after aeration with oxygen or with nitrogen issubjected to photoillumination to cause photo-luminescence. Theluminescence is judged to be phosphorescence if almost no luminescenceattributable to the compound is observed with respect to the solutionaerated with oxygen but photo-luminescence is confirmed with respect tothe solution aerated with nitrogen. In contrast thereto, in the case offluorescence, luminescence attributable to the compound does notdisappear even with respect to the solution aerated with oxygen. Thephosphorescence of all the compounds of the present invention has beenconfirmed by this method unless otherwise noted specifically.

(2) Phosphorescence yield (a relative quantum yield, i.e., a ratio of anobjective sample's quantum yield Φ(sample) to a standard sample'squantum yield Φ(st)) is determined according to the following formula:Φ(sample)/Φ(st)=[Sem(sample)/Iabs(sample)]/[Sem(st)/Iabs(st)],wherein Iabs(st) denotes an absorption coefficient at an excitationwavelength of the standard sample; Sem(st), a luminescence spectralareal intensity when excited at the same wavelength: labs(sample), anabsorption coefficient at an excitation wavelength of an objectivecompound; and Sem(sample), a luminescence spectral areal intensity whenexcited at the same wavelength.

Phosphorescence yield values described herein are relative values withrespect a phosphorescence yield Φ=1 of Ir(ppy)₃ as a standard sample.

(3) A method of measurement of phosphorescence life is as follows.

A sample compound is dissolved in chloroform and spin-coated onto aquartz substrate in a thickness of ca. 0.1 μm and is exposed topulsative nitrogen laser light at an excitation wavelength of 337 nm atroom temperature by using a luminescence life meter (made by HamamatsuPhotonics K.K.) After completion of the excitation pulses, the decaycharacteristic of luminescence intensity is measured.

When an initial luminescence intensity is denoted by I₀, a luminescenceintensity after t(sec) is expressed according to the following formulawith reference to a luminescence life τ(sec):I=I ₀·exp(−t/τ).

Thus, the luminescence life τ is a time period in which the luminescenceintensity I is attenuated down to 1/e of the initial intensity I(I/I₀=e⁻¹, e is a base of natural logarithm). A luminescence life of 80nsec or longer, particularly 100 nsec or longer, is a second conditionto be judged as phosphorescence, whereas fluorescence shows a shorterluminescence life on the order of several tens nsec or shorter.

The luminescence material exhibited high phosphorescence quantum yieldsof 0.15 to 0.9 and short phosphorescence lives of 0.1 to 10 μsec. Ashort phosphorescence life becomes a condition for causing little energydeactivation and exhibiting an enhanced luminescence efficiency. Morespecifically if the phosphorescence life is long, the number of tripletstate molecules maintained for luminescence is increased, and thedeactivation process is liable to occur, thus resulting in a lowerluminescence efficiency particularly at the time of a high-currentdensity. The material of the present invention has a relatively shortphosphorescence life thus exhibiting a high phosphorescence quantumyield, and is therefore suitable as a luminescence material for an ELdevice. The present inventors further consider that the improvedperformance is attributable to the following.

A difference between a photo-absorption spectrum peak wavelength causedby transition from a single ground state to an excited triplet state anda maximum peak wavelength of luminescence spectrum is generally called aStokes' shift. The difference in peak wavelength is considered to becaused by a change in energy state of triplet excitons affected by otherground state energy levels. The change in energy state is associatedwith the Stokes' shift, and a larger amount of the shift generallyresults in a lowering in maximum luminescence intensity and a broadeningof luminescence spectrum leading to a deterioration in monochromaticityof luminescence color. This effect appears particularly remarkably in ared region having a short transition width from the singlet to thetriplet.

For example, as for the isoquinoline-type iridium complexes of thepresent invention, tris(1-phenylisoquinoline-C²,N)iridium (III) (ExampleCompound No. 1 in Tables 1 to 23 appearing hereafter; abbreviated asIr(PiQ)₃), tris[1-(2-thienyl)-isoquinoline-C³,N]iridium (III) (ExampleCompound No. 24, abbreviated as Ir(tiQ)₃), andtris[1-(9,9-dizaethylfluorene-2-yl)isoquinoline-C³,N]iridium (III)(Example Compound 28, abbreviated as Ir(FliQ)₃) exhibited Stokes' shiftsof 37 nm, 55 cm and 33 nm, respectively, and relative quantum yields of0.66, 0.43 and 0.48, respectively.

On the other hand, as for non-isoquinoline-type red luminescencematerials, tris[1-thianaphthene-2-yl)pyridine-C³,N]iridium (III)(abbreviated as Ir(BrP)₃) andtris[1-(thianaphthene-2-yl)-4-trifluoromethylpyridine (abbreviated asIr(Bt₅CF₃Py)₃) exhibited remarkably longer Stokes' shifts of 132 nm and85 nm, respectively, and lower relative quantum yields of 0.29 and 0.12,respectively, compared with the compounds of the present invention.

Even such non-isoquinoline-type red luminescence materials show highquantum yields not achieved by conventional materials, red luminescencematerials showing a smaller Stokes' shift, like isoquinoline-typeiridium complexes of the present invention, are found to have a tendencyof having a still higher quantum yield. A smaller Stokes' shift isconsidered to provide a larger velocity constant of energy radiation, ashorter phosphorescence life and therefore a higher luminescenceefficiency. Based on the above consideration, the introduction ofisoquinoline is considered to result in a small Stokes' shift, anenhanced luminescence quantum yield and a better chromaticity.

<<Nomenclature and Structural Expression of Compounds>>

Now, some explanation is added to the manner of structuralidentification of a metal coordination compound of the present inventionand the manner of allotting atomic position number as a basis thereforwith reference to Ir(PiQ)₃ (Example Compound No. 1), for example. Themetal coordination compound has a ligand of 1-phenylisoquinoline ofwhich position numbers are allotted as follows:

Accordingly, Ir(PiQ)₃ formed by coordination of three1-phenylisoquinoline molecules onto iridium with the position-2 carbonatom of the phenyl group and the nitrogen atom of the isoquinoline ringis named as tris(1-phenylisoquinoline-C²,N)iridium (III).

Ir(PiQ)₃ exhibits a high quantum yield as mentioned above, but it hasbeen also found that Ir(PiQ)₃ provided with an additional substituentshows a further higher quantum yield in a solution or a solid statefilm. For example, a class oftris[1-alkylphenyl)isoquinoline-C²,N]iridium (III) formed by attachingalkyl substituents at position-4 of the basic ligand skeleton of1-phenylisoquinoline exhibits still higher relative quantum yields(i.e., quantum yields when Ir(ppy)₃ in a dilute solution in toluene istaken to have a quantum yield of 1). More specifically, the class ofcompounds have been found to exhibit quantum yields as shown belowdepending on species of the alkyl substituents. Remarkable increases inquantum yield have been recognized at number of carbon atoms of 4 ormore in the subsequent group.

(1) —CH₃=0.64

(2) —C(CH₃)₃=0.7

(3) —C₄H₉=0.82

(4) —C₆H₁₃=0.88

(5) —C₈H₁₇=0.72

From the above results, the addition of a substituent to the aboveskeleton to weaken the inter-molecular interaction is found to beeffective for increasing the luminescence quantum yield.

On the other hand, in the case of using resistance heating vacuumdeposition using a tungsten boat for device formation, a material havinga molecular weight of at most 1000 has been found suitable in view ofthe device production process characteristic, such as possibility ofvacuum deposition at a low current and a high rate.

More specifically, the above-mentioned class of alkyl chain-addediridium complexes have a tendency of exhibiting a higher vacuumdeposition temperature at the time of device formation. The entiremolecular weights of thus-alkyl-substituted Ir(PiQ)₃ derivatives are asfollows depending on the species of alkyl substituents as follows.

(1) —CH₃=847

(2) —C(CH₃)₃=973

(3) —C₄H₉=973

(4) —C₆H₁₃=1058

(5) —C₈H₁₇=1141

At the time of resistance heating vacuum deposition at 10⁻⁴ Pa, thesematerials required necessary currents for vacuum deposition as followsdepending an the species of alkyl substituents.

(1) —CH₃=58 amperes

(2) —C(CH₃)₃=61 amperes

(3) —C₄H₉=61 amperes

(4) —C₆H₁₃=64 amperes

(5) —C₈H₁₇=67 amperes

Further, a metal coordination compound having a substituent of fluorineatom or a polyfluorinated alkyl can weaken the intermolecularinteraction owing to fluorine atoms to lower the vacuum depositiontemperature, and is advantageous in that a metal coordination compoundof a larger molecular weight can be used as a luminescence materialwithout impairing the vacuum deposition characteristic. For example, thesubstitution of a trifluoromethyl group for one methyl group can lowerthe vacuum deposition temperature by ca. 1° C. while the molecularweight is rather increased thereby.

By introducing an isoquinoline skeleton in a metal coordination compoundhaving a structure of a type represented by the above formula (1) or(9), the luminescence wavelength can be adjusted, and it has been foundthat the metal coordination compound of the present invention whereinthe isoquinoline skeleton is bonded to the cyclic group A at itsposition-1, is unexpectedly advantageous for increasing the luminescencewavelength (i.e., providing red luminescence).

On the other hand, while a known compound oftetrakis(2-phenylpyridine-C²,N) (μ-dichloro)diiridium (III) does notprovide a substantial luminescence spectrum, a metal coordinationcompound of the formula (7) having introduced an isoquinoline skeletonhas exhibited a strong luminescence spectrum. From this fact, it isunderstood that a metal coordination compound of the formula (7) is alsosuited as a luminescence material for an EL device.

Further, by introducing an electron-attractive substituent or anelectron-donative substituent to the metal coordination compound of thepresent invention, it is possible to adjust the luminescence wavelength.Further, by introducing a substituent group, such as an alkoxy group ora polyfluoroalkyl group, having a large electronic effect and also astereo-scopically large bulk volume, it becomes possible to effect botha control of luminescence wavelength and a suppression of densityextinction due to inter-molecular interaction. Further, the introductionof a substituent group having little electronic effect but having astereoscopically large bulk volume, such as an alkyl group, isconsidered to be able to suppress the density extraction withoutchanging the luminescence wavelength.

Further, by replacing one or two CH groups in the isoquinoline ring of ametal coordination compound represented by the formula (1) or (9), theluminescence wavelength can be adjusted without introducing asubstituent group.

Also from the above viewpoints, the metal coordination compound of thepresent invention is suited as a luminescence material for an organic ELdevice.

Further, a thermal stability is an important property for an organicmaterial constituting an organic EL device. The thermal stabilityseriously affects the production stability at the time of deviceproduction and device stability during operation under current supply.For preparation of organic EL devices, a process of vacuum deposition,spin coating or ink jetting is contemplated. Particularly, in the vacuumdeposition process, an organic material is subjected to high temperaturefor certain period for vaporizing the organic material by sublimation orevaporation and is deposited onto the substrate. Accordingly, thethermal stability of a component material is very important.

Further, also at the time of supplying electricity to the device forcausing luminescence, a Joule's heat is locally generated due to passageof a high current. If a component material has a low thermal stability,the material can cause a device deterioration due to such heat. Forexample, the above-mentioned Ir(PiQ)₃ andbis(1-phenylisoquinoline-C²,N)(acetylacetonato)iridium (III) (ExampleCompound No. 42, abbreviated as Ir(PiQ)₂acac) exhibited decompositiontemperatures of 380° C. and 340° C., respectively, under nitrogen flow,thus providing a substantial difference in decomposition temperature.More specifically, under a certain vacuum deposition condition,Ir(PiQ)₃acac caused an appreciable decomposition in a vacuum depositionchamber, but Ir(PiQ)₃ did not cause appreciable decomposition under thesame condition. As a result of measurement of decomposition degree undervarious conditions of vacuum deposition, Ir(PiQ)₃ acac exhibited lowerupper limits in vacuum deposition speed or degree of vacuum in vacuumdeposition, thus exhibiting a narrower production margin at the time ofmass production. In this way, a material thermal stability seriouslyaffects the productivity.

In a comparative test, EL devices were prepared from the above-mentionedtwo luminescence materials through vacuum deposition underdecomposition-free condition and subjected to evaluation of luminancedeterioration. As a result, when electricity supply was started toprovide an initial luminance of 5000 cd/m², Ir(PiQ)₃ and Ir(PiQ)₂ acacexhibited luminance half-attenuation periods in a ratio of ca. 3:1, sothat Ir(PiQ)₃ was substantially stable against electricity supply asrepresented by a longer luminance half-attenuation period. In this way,the thermal stability of a component material is a factor determiningthe production stability and performance stability of a device, so thata material having a high thermal stability is desired.

It is believed that the ligand of the present invention, as a result ofintroduction of isoquinoline skeleton, has a rigid molecular structure,so as to suppress the formation of an excitation-associated moleculeresulting in thermal deactivation, thus suppressing energy deactivationdue to molecular movement. Further, it is also believed that extinctionprocesses are reduced to result in an improved device performance. In anactual current conduction test, the luminescence material of the presentinvention, i.e., a metal coordination compound having a ligandcomprising an isoquinoline skeleton bonded to a cyclic group A at its1-position, showed a high stability.

More specifically, a tris(1-substituted isoquinolyl)-metal coordinationcompound of n=0 in the formula (3) is generally preferred in view ofexcellent thermal stability.

Accordingly, a luminescence material having a luminescence wavelength oflong-wavelength region (red luminescence) and a high chemical stabilityas well as a high luminescence efficiency has not been realizedheretofore but can be realized by the luminescence material of thepresent invention.

A high-efficiency luminescence device having a layer structure as shownin FIGS. 1(a), (b) and (c) of the present invention is applicable to aproduct requiring energy economization or a high luminance. Morespecifically, the luminescence device is applicable to a displayapparatus, an illumination apparatus, a printer light source or abacklight for a luminescence layer display apparatus. As a displayapparatus, it allows a flat panel display, which is light in weight andprovides a highly recognizable display at a low energy consumption. As aprinter light source, the luminescence device of the present inventioncan be used instead of a laser light source of a laser beam printer. Forthe illumination apparatus or backlight, the energy economization effectaccording to the present invention can be utilized.

For the application to a display, a drive system using a thin-filmtransistor (abbreviated as TFT) drive circuit according to an activematrix-scheme, may be used. Hereinbelow, an embodiment of using a deviceof the present invention in combination with an active matrix substrateis briefly described with reference to FIG. 4.

FIG. 4 illustrates an embodiment of panel structure comprising an ELdevice and drive means. The panel is provided with a scanning signaldriver, a data signal driver and a current supply source which areconnected to gate selection lines, data signal lines and current supplylines, respectively. At each intersection of the gate selection linesand the data signal lines, a display pixel electrode is disposed. Thescanning signal drive sequentially selects the gate selection lines G1,G2, G3 . . . Gn, and in synchronism herewith, picture signals aresupplied from the data signal driver to display a printer.

TFT switching devices are not particularly restricted, and devices of asingle crystal-silicon substrate, MIM devices or devices of a-Si typecan be easily applied.

On the ITO electrodes, one or more organic EL layers and a cathode layerare sequentially disposed to provide an organic EL display panel. Bydriving a display panel including a luminescence layer comprising aluminescence material of the present invention, it becomes possible toprovide a display which exhibits a good picture quality and is stableeven for a long period display.

<<Brief Description of Synthesis Path>>

Some synthetic paths for providing a metal coordination compoundrepresented by the above-mentioned formula (1) are illustrated belowwith reference to an iridium coordination compound for example:

Some specific structural examples of metal coordination compounds usedin the present invention are shown in Tables 1 to Tables 23 appearinghereinafter, which are however only representative examples and are notexhaustive. Ph to Iq10 shown in Tables 1 to 23 represent partialstructures shown below, corresponding to the above-mentioned formula (3)(or partial structures therein represented by formulae (2), and (4)-(6))or formula (3). Further, R1-R10 represent substituents in the Ph toIq10, and E, G and J represent substituents in the formula (5).

TABLE 1 A B Nu M m n A B R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 1 Ir 3 0 Ph Iq2H H H H H H H H H H 2 Ir 3 0 Ph Iq2 H

H H H H H H H H 3 Ir 3 0 Ph Iq2 H H

H H H H H H H 4 Ir 3 0 Ph Iq2 H

H H H

H H H H 5 Ir 3 0 Ph Iq2 H CH3 H H H H CF3 H H H 6 Ir 3 0 Ph Iq2 H H CH3H H CF3 H H H H 7 Ir 3 0 Ph Iq2 H

H H H H H H H H 8 Ir 3 0 Ph Iq2 H H

H H H H H H H 9 Ir 3 0 Ph Iq2 H

H H H H H H H H 10 Ir 3 0 Ph Iq2 H H

H H H H H H H

TABLE 2 A B No M m n A B R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 11 Ir 3 0 Ph Iq2H CF3 H H H H H H H H 12 Ir 3 0 Ph Iq2 H H CF3 H H H H H H H 13 Ir 3 0Ph Iq2 H

H H H H H H H H 14 Ir 3 0 Ph Iq2 H H

H H H H H H H 15 Ir 3 0 Ph Iq2 H

H H H H H H H H 16 Ir 3 0 Ph Iq2 H

H H H H H H H H 17 Ir 3 0 Ph Iq2 H OCH3 H H H H H H H H 18 Ir 3 0 Ph Iq2H

H H H

H H H H

TABLE 3 A No M m n A B A′ B′ E G J R1 R2 R3 R4 19 Ir 3 0 Ph Iq2 — — — —— H CH3 H H 20 Ir 3 0 Ph Iq2 — — — — — H H CH3 H 21 Ir 3 0 Ph Iq2 — — —— — H CH3 CH3 H 22 Ir 3 0 Ph Iq2 — — — — — H F H H 23 Ir 3 0 Ph Iq2 — —— — — H H F H 24 Ir 3 0 Tn1 Iq2 — — — — — H H — — 25 Ir 3 0 Tn3 Iq2 — —— — — H H — — 26 Ir 3 0 Tn4 Iq2 — — — — — H H — — 27 Ir 3 0 Np2 Iq2 — —— — — H H — — 28 Ir 3 0 Fl Iq2 — — — — — H H — — 29 Ir 3 0 Ph Iq5 — — —— — H H H H 30 Ir 3 0 Fl Iq5 — — — — — H H H H 31 Ir 2 1 Ph Iq2 Ph Pr —— — H H H H 32 Ir 2 1 Ph Iq2 Ph Pr — — — H CH3 H H 33 Ir 2 1 Ph Iq2 PhPr — — — H H CH3 H 34 Ir 2 1 Ph Iq2 Ph Pr — — — H CH3 CH3 H 35 Ir 2 1 PhIq2 Ph Pr — — — H F H H 36 Ir 2 1 Ph Iq2 Ph Pr — — — H H F H 37 Ir 2 1Tn1 Iq2 Ph Pr — — — H H — — 38 Ir 2 1 Tn3 Iq2 Ph Pr — — — H H — — 39 Ir2 1 Tn4 Iq2 Ph Pr — — — H H — — 40 Ir 2 1 Np2 Iq2 Ph Pr — — — H H — — 41Ir 2 1 Fl Iq2 Ph Pr — — — H H — — 42 Ir 2 1 Ph Iq2 — — CH3 CH3 H H H H H43 Ir 2 1 Ph Iq2 — — CH3 CH3 H H CH3 H H 44 Ir 2 1 Ph Iq2 — — CH3 CH3 HH H CH3 H 45 Ir 2 1 Ph Iq2 — — CH3 CH3 H H CH3 CH3 H 46 Ir 2 1 Ph Iq2 —— CH3 CH3 H H F H H 47 Ir 2 1 Ph Iq2 — — CH3 CH3 H H H F H 48 Ir 2 1 Tn1Iq2 — — CH3 CH3 H H H — — 49 Ir 2 1 Tn3 Iq2 — — CH3 CH3 H H H — — 50 Ir2 1 Tn4 Iq2 — — CH3 CH3 H H H — — 51 Ir 2 1 Np2 Iq2 — — CH3 CH3 H H H —— 52 Ir 2 1 Fl Iq2 — — CH3 CH3 H H H — — 53 Ir 2 1 Ph Iq2 — — CF3 CF3 HH H H H 54 Ir 2 1 Ph Iq2 — — CF3 CF3 H H CH3 H H 55 Ir 2 1 Ph Iq2 — —CF3 CF3 H H H CH3 H 56 Ir 2 1 Ph Iq2 — — CF3 CF3 H H CH3 CH3 H 57 Ir 2 1Ph Iq2 — — CF3 CF3 H H F H H 58 Ir 2 1 Ph Iq2 — — CF3 CF3 H H H F H 59Ir 2 1 Tn1 Iq2 — — CF3 CF3 H H H — — 60 Ir 2 1 Tn3 Iq2 — — CF3 CF3 H H H— — A′ B B′ No R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 19 — — — — H HH H H H — — — — 20 — — — — H H H H H H — — — — 21 — — — — H H H H H H —— — — 22 — — — — H H H H H H — — — — 23 — — — — H H H H H H — — — — 24 —— — — H H H H H H — — — — 25 — — — — H H H H H H — — — — 26 — — — — H HH H H H — — — — 27 — — — — H H H H H H — — — — 28 — — — — H H H H H H —— — — 29 — — — — — H H H H H — — — — 30 — — — — — H H H H H — — — — 31 HH H H H H H H H H H H H H 32 H H H H H H H H H H H H H H 33 H H H H H HH H H H H H H H 34 H H H H H H H H H H H H H H 35 H H H H H H H H H H HH H H 36 H H H H H H H H H H H H H H 37 H H H H H H H H H H H H H H 38 HH H H H H H H H H H H H H 39 H H H H H H H H H H H H H H 40 H H H H H HH H H H H H H H 41 H H H H H H H H H H H H H H 42 — — — — H H H H H H —— — — 43 — — — — H H H H H H — — — — 44 — — — — H H H H H H — — — — 45 —— — — H H H H H H — — — — 46 — — — — H H H H H H — — — — 47 — — — — H HH H H H — — — — 48 — — — — H H H H H H — — — — 49 — — — — H H H H H H —— — — 50 — — — — H H H H H H — — — — 51 — — — — H H H H H H — — — — 52 —— — — H H H H H H — — — — 53 — — — — H H H H H H — — — — 54 — — — — H HH H H H — — — — 55 — — — — H H H H H H — — — — 56 — — — — H H H H H H —— — — 57 — — — — H H H H H H — — — — 58 — — — — H H H H H H — — — — 59 —— — — H H H H H H — — — — 60 — — — — H H H H H H — — — —

TABLE 4 A A′ No M m n A B A′ B′ E G J R1 R2 R3 R4 R1 R2 R3 R4 61 Ir 2 1Tn4 Iq2 — — CF3 CF3 H H H — — — — — — 62 Ir 2 1 Np2 Iq2 — — CF3 CF3 H HH — — — — — — 63 Ir 2 1 Fl Iq2 — — CF3 CF3 H H H — — — — — — 64 Ir 1 2Ph Iq2 Ph Pr — — — H H H H H H H H 65 Ir 1 2 Ph Iq2 Ph Pr — — — H CH3 HH H H H H 66 Ir 1 2 Ph Iq2 Ph Pr — — — H H CH3 H H H H H 67 Ir 1 2 PhIq2 Ph Pr — — — H CH3 CH3 H H H H H 68 Ir 1 2 Ph Iq2 Ph Pr — — — H F H HH H H H 69 Ir 1 2 Ph Iq2 Ph Pr — — — H H F H H H H H 70 Ir 1 2 Tn1 Iq2Ph Pr — — — H H — — H H H H 71 Ir 1 2 Tn3 Iq2 Ph Pr — — — H H — — H H HH 72 Ir 1 2 Tn4 Iq2 Ph Pr — — — H H — — H H H H 73 Ir 1 2 Np2 Iq2 Ph Pr— — — H H — — H H H H 74 Ir 1 2 Fl Iq2 Ph Pr — — — H H — — H H H H 75 Ir1 2 Ph Iq2 — — CH3 CH3 H H H H H — — — — 76 Ir 1 2 Ph Iq2 — — CH3 CH3 HH CH3 H H — — — — 77 Ir 1 2 Ph Iq2 — — CH3 CH3 H H H CH3 H — — — — 78 Ir1 2 Ph Iq2 — — CH3 CH3 H H CH3 CH3 H — — — — 79 Ir 1 2 Ph Iq2 — — CH3CH3 H H F H H — — — — 80 Ir 1 2 Ph Iq2 — — CH3 CH3 H H H F H — — — — 81Ir 3 0 Ph Iq2 — — — — — H H H H — — — — 82 Ir 3 0 Ph Iq2 — — — — — H H HH — — — — 83 Ir 3 0 Ph Iq2 — — — — — H H H H — — — — 84 Ir 3 0 Ph Iq2 —— — — — H H F H — — — — 85 Ir 3 0 Ph Iq2 — — — — — H H F H — — — — 86 Rh3 0 Ph Iq2 — — — — — H H H H — — — — 87 Rh 3 0 Tn1 Iq2 — — — — — H H — —— — — — 88 Rh 3 0 Tn3 Iq2 — — — — — H H — — — — — — 89 Rh 3 0 Np2 Iq2 —— — — — H H — — — — — — 90 Rh 3 0 Fl Iq2 — — — — — H H — — — — — — 91 Rh2 1 Ph Iq2 Ph Pr — — — H H H H H H H H 92 Rh 2 1 Ph Iq2 Ph Pr — — — HCH3 H H H H H H 93 Rh 2 1 Ph Iq2 Ph Pr — — — H H CH3 H H H H H 94 Rh 2 1Ph Iq2 — — CH3 CH3 H H H H H — — — — 95 Pt 2 0 Ph Iq2 — — — — — H H H H— — — — 96 Pt 2 0 Ph Iq2 — — — — — H CH3 H H — — — — 97 Pt 2 0 Ph Iq2 —— — — — H CH3 CH3 H — — — — 98 Pt 2 0 Ph Iq2 — — — — — H F H H — — — —99 Pt 2 0 Ph Iq2 — — — — — H H F H — — — — 100  Pt 2 0 Tn1 Iq2 — — — — —H H — — — — — — B B′ No R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 61 H H H H H H —— — — 62 H H H H H H — — — — 63 H H H H H H — — — — 64 H H H H H H H H HH 65 H H H H H H H H H H 66 H H H H H H H H H H 67 H H H H H H H H H H68 H H H H H H H H H H 69 H H H H H H H H H H 70 H H H H H H H H H H 71H H H H H H H H H H 72 H H H H H H H H H H 73 H H H H H H H H H H 74 H HH H H H H H H H 75 H H H H H H — — — — 76 H H H H H H — — — — 77 H H H HH H — — — — 78 H H H H H H — — — — 79 H H H H H H — — — — 80 H H H H H H— — — — 81 H H H H F H — — — — 82 H H H H CF3 H — — — — 83 H H H CF3 H H— — — — 84 H H H F H H — — — — 85 H H H CF3 H H — — — — 86 H H H H H H —— — — 87 H H H H H H — — — — 88 H H H H H H — — — — 89 H H H H H H — — —— 90 H H H H H H — — — — 91 H H H H H H H H H H 92 H H H H H H H H H H93 H H H H H H H H H H 94 H H H H H H — — — — 95 H H H H H H — — — — 96H H H H H H — — — — 97 H H H H H H — — — — 98 H H H H H H — — — — 99 H HH H H H — — — — 100  H H H H H H — — — —

TABLE 5 A No M m n A B A′ B′ E G J R1 R2 R3 R4 101 Pt 2 0 Tn3 Iq2 — — —— — H H — — 102 Pt 1 1 Ph Iq2 Ph Pr — — — H H H H 103 Pt 1 1 Ph Iq2 PhPr — — — H H CH3 H 104 Pt 1 1 Ph Iq2 Ph Pr — — — H CH3 CH3 H 105 Pt 1 1Ph Iq2 Ph Pr — — — H F H H 106 Pd 2 0 Ph Iq2 — — — — — H H H H 107 Pd 20 Ph Iq2 — — — — — H H CH3 H 108 Pd 2 0 Tn1 Iq2 — — — — — H H — — 109 Pd2 0 Tn3 Iq2 — — — — — H H — — 110 Pd 1 1 Ph Iq2 Ph Pr — — — H H H H 111Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 H H H H 112 Ir 2 1 Ph Iq2 — — C(CH3)3C(CH3)3 H H H H H 113 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 H H H H 114 Ir 2 1Tn1 Iq2 — — CH3 CH3 CH3 H H — — 115 Ir 2 1 Tn1 Iq2 — — C(CH3)3 C(CH3)3 HH H — — 116 Ir 2 1 Tn1 Iq2 — — CH3 C3H7 CH3 H H — — 117 Ir 2 1 Tn2 Iq2 —— CH3 CH3 CH3 H H — — 118 Ir 2 1 Tn2 Iq2 — — C(CH3)3 C(CH3)3 H H H — —119 Ir 2 1 Tn2 Iq2 — — CH3 C6H13 CH3 H H — — 120 Ir 2 1 Tn3 Iq2 — — CH3CH3 CH3 H H — — 121 Ir 2 1 Tn3 Iq2 — — C(CH3)3 C(CH3)3 H H H — — 122 Ir2 1 Tn3 Iq2 — — CH3 C4H9 CH3 H H — — 123 Ir 2 1 Tn4 Iq2 — — CH3 CH3 CH3H H — — 124 Ir 2 1 Tn4 Iq2 — — C(CH3)3 C(CH3)3 H H H — — 125 Ir 2 1 Tn4Iq2 — — CH3 C5H11 CH3 H H — — 126 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 H CH3 HH 127 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H H CH3 H H 128 Ir 2 1 Ph Iq2 —— CH3 C4H9 CH3 H CH3 H H 129 Ir 2 1 Fl Iq2 — — CH3 CH3 CH3 H H — — 130Ir 2 1 Fl Iq2 — — C(CH3)3 C(CH3)3 H H H — — 131 Ir 2 1 Fl Iq2 — — CH3C4H9 CH3 H H — — 132 Ir 2 1 Np1 Iq2 — — CH3 CH3 CH3 H H — — 133 Ir 2 1Np1 Iq2 — — C(CH3)3 C(CH3)3 H H H — — 134 Ir 2 1 Np1 Iq2 — — CH3 C4H9CH3 H H — — 135 Ir 3 0 Ph Iq2 — — — — — H C2H5 H H 136 Ir 2 1 Ph Iq2 PhPr — — — H C2H5 H H 137 Ir 2 1 Ph Iq2 — — CH3 CH3 H H C2H5 H H 138 Ir 21 Ph Iq2 — — CH3 CH3 CH3 H C2H5 H H 139 Ir 2 1 Ph Iq2 — — C(CH3)3C(CH3)3 H H C2H5 H H 140 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 H C2H5 H H A′ BB′ No R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 101 — — — — H H H H H H— — — — 102 H H H H H H H H H H H H H H 103 H H H H H H H H H H H H H H104 H H H H H H H H H H H H H H 105 H H H H H H H H H H H H H H 106 — —— — H H H H H H — — — — 107 — — — — H H H H H H — — — — 108 — — — — H HH H H H — — — — 109 — — — — H H H H H H — — — — 110 H H H H H H H H H HH H H H 111 — — — — H H H H H H — — — — 112 — — — — H H H H H H — — — —113 — — — — H H H H H H — — — — 114 — — — — H H H H H H — — — — 115 — —— — H H H H H H — — — — 116 — — — — H H H H H H — — — — 117 — — — — H HH H H H — — — — 118 — — — — H H H H H H — — — — 119 — — — — H H H H H H— — — — 120 — — — — H H H H H H — — — — 121 — — — — H H H H H H — — — —122 — — — — H H H H H H — — — — 123 — — — — H H H H H H — — — — 124 — —— — H H H H H H — — — — 125 — — — — H H H H H H — — — — 126 — — — — H HH H H H — — — — 127 — — — — H H H H H H — — — — 128 — — — — H H H H H H— — — — 129 — — — — H H H H H H — — — — 130 — — — — H H H H H H — — — —131 — — — — H H H H H H — — — — 132 — — — — H H H H H H — — — — 133 — —— — H H H H H H — — — — 134 — — — — H H H H H H — — — — 135 — — — — H HH H H H — — — — 136 H H H H H H H H H H H H H H 137 — — — — H H H H H H— — — — 138 — — — — H H H H H H — — — — 139 — — — — H H H H H H — — — —140 — — — — H H H H H H — — — —

TABLE 6 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 R3 R4 141 Ir2 1 Ph Iq2 — — — — — Pr H C2H5 H H — — — — 142 Ir 2 1 Ph Iq2 — — — — —Pr H C2H5 H H — — — — 143 Ir 2 1 Ph Iq2 — — — — — Iq2 H C2H5 H H — — — —144 Ir 3 0 Ph Iq2 — — — — — — H C3H7 H H — — — — 145 Ir 3 0 Ph Iq2 — — —— — — H C3H7 H H — — — — 146 Ir 3 0 Ph Iq2 — — — — — — H CH(CH3)2 H H —— — — 147 Ir 2 1 Ph Iq2 Ph Pr — — — — H C3H7 H H H H H H 148 Ir 2 1 PhIq2 — — CH3 CH3 H — H C3H7 H H — — — — 149 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3— H C3H7 H H — — — — 150 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H C3H7 HH — — — — 151 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H C3H7 H H — — — — 152 Ir2 1 Ph Iq2 — — — — — Pr H C3H7 H H — — — — 153 Ir 2 1 Ph Iq2 — — — — —Pr H C3H7 H H — — — — 154 Ir 2 1 Ph Iq2 — — — — — Iq2 H C3H7 H H — — — —155 Ir 3 0 Ph Iq2 — — — — — — H H H H — — — — 156 Ir 3 0 Ph Iq2 — — — —— — H H H H — — — — 157 Ir 3 0 Ph Iq2 — — — — — — H CH3 H H — — — — 158Ir 3 0 Ph Iq2 — — — — — — H CH3 H H — — — — 159 Ir 3 0 Ph Iq2 — — — — —— H C4H9 H H — — — — 160 Ir 3 0 Ph Iq2 — — — — — — H C4H9 H H — — — —161 Ir 3 0 Ph Iq2 — — — — — — H C4H9 H H — — — — 162 Ir 2 1 Ph Iq2 Ph Pr— — — — H C4H9 H H H H H H 163 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H C4H9 H H— — — — 164 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — H C4H9 H H — — — — 165 Ir 21 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H C4H9 H H — — — — 166 Ir 2 1 Ph Iq2 —— CH3 C4H9 CH3 — H C4H9 H H — — — — 167 Ir 2 1 Ph Iq2 — — — — — Pr HC4H9 H H — — — — 168 Ir 2 1 Ph Iq2 — — — — — Pr H C4H9 H H — — — — 169Ir 2 1 Ph Iq2 — — — — — Iq2 H C4H9 H H — — — — 170 Ir 3 0 Ph Iq2 — — — —— — H C(CH3)3 H H — — — — 171 Ir 3 0 Ph Iq2 — — — — — — H C(CH3)3 H H —— — — 172 Ir 3 0 Ph Iq2 — — — — — — H C(CH3)3 H H — — — — 173 Ir 2 1 PhIq2 Ph Pr — — — — H C(CH3)3 H H H H H H 174 Ir 2 1 Ph Iq2 — — CH3 CH3 H— H C(CH3)3 H H — — — — 175 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — H C(CH3)3 HH — — — — 176 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H C(CH3)3 H H — — —— 177 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H C(CH3)3 H H — — — — 178 Ir 2 1Ph Iq2 — — — — — Pr H C(CH3)3 H H — — — — 179 Ir 2 1 Ph Iq2 — — — — — PrH C(CH3)3 H H — — — — 180 Ir 2 1 Ph Iq2 — — — — — Iq2 H C(CH3)3 H H — —— — B B′ B″ No R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R5 R6 R7 R8 R9 R10 141 H HH H H H — — — — H H H H — — 142 H H H H H H — — — — H H C4H9 H — — 143 HH H H H H — — — — H H H H H H 144 H H H H H H — — — — — — — — — — 145 HH H F H H — — — — — — — — — — 146 H H H H H H — — — — — — — — — — 147 HH H H H H H H H H — — — — — — 148 H H H H H H — — — — — — — — — — 149 HH H H H H — — — — — — — — — — 150 H H H H H H — — — — — — — — — — 151 HH H H H H — — — — — — — — — — 152 H H H H H H — — — — H H H H — — 153 HH H H H H — — — — H H C4H9 H — — 154 H H H H H H — — — — H H H H H H 155H H H F H H — — — — — — — — — — 156 H H H H C6H13 H — — — — — — — — — —157 H H H F H H — — — — — — — — — — 158 H H H H C6H13 H — — — — — — — —— — 159 H H H H H H — — — — — — — — — — 160 H H H F H H — — — — — — — —— — 161 H H H H C6H13 H — — — — — — — — — — 162 H H H H H H H H H H — —— — — — 163 H H H H H H — — — — — — — — — — 164 H H H H H H — — — — — —— — — — 165 H H H H H H — — — — — — — — — — 166 H H H H H H — — — — — —— — — — 167 H H H H H H — — — — H H H H — — 168 H H H H H H — — — — H HC4H9 H — — 169 H H H H H H — — — — H H H H H H 170 H H H H H H — — — — —— — — — — 171 H H H F H H — — — — — — — — — — 172 H H H H C6H13 H — — —— — — — — — — 173 H H H H H H H H H H — — — — — — 174 H H H H H H — — —— — — — — — — 175 H H H H H H — — — — — — — — — — 176 H H H H H H — — —— — — — — — — 177 H H H H H H — — — — — — — — — — 178 H H H H H H — — —— H H H H — — 179 H H H H H H — — — — H H C4H9 H — — 180 H H H H H H — —— — H H H H H H

TABLE 7 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 R3 R4 181 Ir3 0 Ph Iq2 — — — — — — H C5H11 H H — — — — 182 Ir 3 0 Ph Iq2 — — — — — —H C5H11 H H — — — — 183 Ir 3 0 Ph Iq2 — — — — — — H C5H11 H H — — — —184 Ir 2 1 Ph Iq2 Ph Pr — — — — H C5H11 H H H H H H 185 Ir 2 1 Ph Iq2 —— CH3 CH3 H — H C5H11 H H — — — — 186 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — HC5H11 H H — — — — 187 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H C5H11 H H— — — — 188 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H C5H11 H H — — — — 189 Ir2 1 Ph Iq2 — — — — — Pr H C5H11 H H — — — — 190 Ir 2 1 Ph Iq2 — — — — —Pr H C5H11 H H — — — — 191 Ir 2 1 Ph Iq2 — — — — — Iq2 H C5H11 H H — — —— 192 Ir 3 0 Ph Iq2 — — — — — — H C6H13 H H — — — — 193 Ir 3 0 Ph Iq2 —— — — — — H C6H13 H H — — — — 194 Ir 3 0 Ph Iq2 — — — — — — H C6H13 H H— — — — 195 Ir 2 1 Ph Iq2 Ph Pr — — — — H C6H13 H H H H H H 196 Ir 2 1Ph Iq2 — — CH3 CH3 H — H C6H13 H H — — — — 197 Ir 2 1 Ph Iq2 — — CH3 CH3CH3 — H C6H13 H H — — — — 198 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — HC6H13 H H — — — — 199 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H C6H13 H H — — —— 200 Ir 2 1 Ph Iq2 — — — — — Pr H C6H13 H H — — — — 201 Ir 2 1 Ph Iq2 —— — — — Pr H C6H13 H H — — — — 202 Ir 2 1 Ph Iq2 — — — — — Iq2 H C6H13 HH — — — — 203 Ir 3 0 Ph Iq2 — — — — — — H C7H15 H H — — — — 204 Ir 3 0Ph Iq2 — — — — — — H C7H15 H H — — — — 205 Ir 3 0 Ph Iq2 — — — — — — HC7H15 H H — — — — 206 Ir 2 1 Ph Iq2 Ph Pr — — — — H C7H15 H H H H H H207 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H C7H15 H H — — — — 208 Ir 2 1 Ph Iq2— — CH3 CH3 CH3 — H C7H15 H H — — — — 209 Ir 2 1 Ph Iq2 — — C(CH3)3C(CH3)3 H — H C7H15 H H — — — — 210 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — HC7H15 H H — — — — 211 Ir 2 1 Ph Iq2 — — — — — Pr H C7H15 H H — — — — 212Ir 2 1 Ph Iq2 — — — — — Pr H C7H15 H H — — — — 213 Ir 2 1 Ph Iq2 — — — —— Iq2 H C7H15 H H — — — — 214 Ir 3 0 Ph Iq2 — — — — — — H C8H17 H H — —— — 215 Ir 3 0 Ph Iq2 — — — — — — H C8H17 H H — — — — 216 Ir 3 0 Ph Iq2— — — — — — H C8H17 H H — — — — 217 Ir 2 1 Ph Iq2 Ph Pr — — — — H C8H17H H H H H H 218 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H C8H17 H H — — — — 219 Ir2 1 Ph Iq2 — — CH3 CH3 CH3 — H C8H17 H H — — — — 220 Ir 3 0 Ph Iq2 — — —— — — H H H H — — — — B B′ B″ No R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R5 R6 R7R8 R9 R10 181 H H H H H H — — — — — — — — — — 182 H H H F H H — — — — —— — — — — 183 H H H H C6H13 H — — — — — — — — — — 184 H H H H H H H H HH — — — — — — 185 H H H H H H — — — — — — — — — — 186 H H H H H H — — —— — — — — — — 187 H H H H H H — — — — — — — — — — 188 H H H H H H — — —— — — — — — — 189 H H H H H H — — — — H H H H — — 190 H H H H H H — — —— H H C4H9 H — — 191 H H H H H H — — — — H H H H H H 192 H H H H H H — —— — — — — — — — 193 H H H F H H — — — — — — — — — — 194 H H H H C6H13 H— — — — — — — — — — 195 H H H H H H H H H H — — — — — — 196 H H H H H H— — — — — — — — — — 197 H H H H H H — — — — — — — — — — 198 H H H H H H— — — — — — — — — — 199 H H H H H H — — — — — — — — — — 200 H H H H H H— — — — H H H H — — 201 H H H H H H — — — — H H C4H9 H — — 202 H H H H HH — — — — H H H H H H 203 H H H H H H — — — — — — — — — — 204 H H H F HH — — — — — — — — — — 205 H H H H C6H13 H — — — — — — — — — — 206 H H HH H H H H H H — — — — — — 207 H H H H H H — — — — — — — — — — 208 H H HH H H — — — — — — — — — — 209 H H H H H H — — — — — — — — — — 210 H H HH H H — — — — — — — — — — 211 H H H H H H — — — — H H H H — — 212 H H HH H H — — — — H H C4H9 H — — 213 H H H H H H — — — — H H H H H H 214 H HH H H H — — — — — — — — — — 215 H H H F H H — — — — — — — — — — 216 H HH H C6H13 H — — — — — — — — — — 217 H H H H H H H H H H — — — — — — 218H H H H H H — — — — — — — — — — 219 H H H H H H — — — — — — — — — — 220H H H C8H17 H H — — — — — — — — — —

TABLE 8 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 R3 R4 221 Ir2 1 Ph Iq2 — — CH3 C4H9 CH3 — H C8H17 H H — — — — 222 Ir 2 1 Ph Iq2 — —CH3 CH3 H — H F CH3 H — — — — 223 Ir 2 1 Ph Iq2 — — — — — Pr H C8H17 H H— — — — 224 Ir 2 1 Ph Iq2 — — — — — Iq2 H C8H17 H H — — — — 225 Ir 3 0Ph Iq2 — — — — — — H C9H19 H H — — — — 226 Ir 3 0 Ph Iq2 — — — — — — H FCH3 H — — — — 227 Ir 3 0 Ph Iq2 — — — — — — H H F H — — — — 228 Ir 3 0Ph Iq2 — — — — — — H F H H — — — — 229 Ir 3 0 Ph Iq2 — — — — — — H F H H— — — — 230 Ir 3 0 Ph Iq2 — — — — — — H F H H — — — — 231 Ir 3 0 Ph Iq2— — — — — — H F H H — — — — 232 Ir 3 0 Ph Iq2 — — — — — — F H F H — — —— 233 Ir 3 0 Ph Iq2 — — — — — — F H F H — — — — 234 Ir 2 1 Ph Iq2 — — —— — Pr H C9H19 H H — — — — 235 Ir 2 1 Ph Iq2 — — — — — Iq2 H C9H19 H H —— — — 236 Ir 3 0 Ph Iq2 — — — — — — H C10H21 H H — — — — 237 Ir 3 0 PhIq2 — — — — — — H C10H21 H H — — — — 238 Ir 3 0 Ph Iq2 — — — — — — HC10H21 H H — — — — 239 Ir 2 1 Ph Iq2 Ph Pr — — — — H C10H21 H H H H H H240 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H H H H — — — — 241 Ir 2 1 Ph Iq2 — —CH3 CH3 CH3 — H C10H21 H H — — — — 242 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3H — H C10H21 H H — — — — 243 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H C10H21 HH — — — — 244 Ir 2 1 Ph Iq2 — — — — — Pr H C10H21 H H — — — — 245 Ir 2 1Ph Iq2 — — — — — Pr H C10H21 H H — — — — 246 Ir 2 1 Ph Iq2 — — — — — Iq2H C10H21 H H — — — — 247 Ir 3 0 Ph Iq2 — — — — — — H C11H23 H H — — — —248 Ir 3 0 Ph Iq2 — — — — — — F H F H — — — — 249 Ir 3 0 Ph Iq2 — — — —— — H H H H — — — — 250 Ir 3 0 Ph Iq2 — — — — — — F F F H — — — — 251 Ir3 0 Ph Iq2 — — — — — — F F F H — — — — 252 Ir 3 0 Ph Iq2 — — — — — — F FF H — — — — 253 Ir 3 0 Ph Iq2 — — — — — — F F F H — — — — 254 Ir 3 0 PhIq2 — — — — — — H CF3 H H — — — — 255 Ir 3 0 Ph Iq2 — — — — — — H CF3 HH — — — — 256 Ir 3 0 Ph Iq2 — — — — — — H CF3 H H — — — — 257 Ir 2 1 PhIq2 — — — — — Iq2 H C11H23 H H — — — — 258 Ir 3 0 Ph Iq2 — — — — — — HC12H25 H H — — — — 259 Ir 3 0 Ph Iq2 — — — — — — H C12H25 H H — — — —260 Ir 3 0 Ph Iq2 — — — — — — H CF3 H H — — — — B B′ B″ No R5 R6 R7 R8R9 R10 R5 R6 R7 R8 R5 R6 R7 R8 R9 R10 221 H H H H H H — — — — — — — — —— 222 H H H H H H — — — — — — — — — — 223 H H H H H H — — — — H H C4H9 H— — 224 H H H H H H — — — — H H H H H H 225 H H H H H H — — — — — — — —— — 226 H H H H H H — — — — — — — — — — 227 H H H H CF3 H — — — — — — —— — — 228 H H H F H H — — — — — — — — — — 229 H H H CF3 H H — — — — — —— — — — 230 H H H H F H — — — — — — — — — — 231 H H H H CF3 H — — — — —— — — — — 232 H H H F H H — — — — — — — — — — 233 H H H CF3 H H — — — —H H H H — — 234 H H H H H H — — — — H H C4H9 H — — 235 H H H H H H — — —— H H H H H H 236 H H H H H H — — — — — — — — — — 237 H H H F H H — — —— — — — — — — 238 H H H H C6H13 H — — — — — — — — — — 239 H H H H H H HH H H — — — — — — 240 H H H F H H — — — — — — — — — — 241 H H H H H H —— — — — — — — — — 242 H H H H H H — — — — — — — — — — 243 H H H H H H —— — — — — — — — — 244 H H H H H H — — — — H H H H — — 245 H H H H H H —— — — H H C4H9 H — — 246 H H H H H H — — — — H H H H H H 247 H H H H H H— — — — — — — — — — 248 H H H H F H — — — — — — — — — — 249 H H H H CF3H — — — — — — — — — — 250 H H H CF3 H H — — — — — — — — — — 251 H H H FH H — — — — — — — — — — 252 H H H H F H — — — — — — — — — — 253 H H H HCF3 H — — — — — — — — — — 254 H H H F H H — — — — — — — — — — 255 H H HCF3 H H — — — — — — — — — — 256 H H H H F H — — — — — — — — — — 257 H HH H H H — — — — H H H H H H 258 H H H H H H — — — — — — — — — — 259 H HH F H H — — — — — — — — — — 260 H H H H CF3 H — — — — — — — — — —

TABLE 9 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 R3 R4 261 Ir2 1 Ph Iq2 Ph Pr — — — — H C12H25 H H H H H H 262 Ir 3 0 Ph Iq2 — — — —— — H H CF3 H — — — — 263 Ir 3 0 Ph Iq2 — — — — — — H H CF3 H — — — —264 Ir 3 0 Ph Iq2 — — — — — — H H CF3 H — — — — 265 Ir 3 0 Ph Iq2 — — —— — — H H CF3 H — — — — 266 Ir 3 0 Ph Iq2 — — — — — — H H CF3 H — — — —267 Ir 3 0 Ph Iq2 — — — — — — F F F F — — — — 268 Ir 3 0 Ph Iq2 — — — —— — F F F F — — — — 269 Ir 3 0 Ph Iq2 — — — — — — H C13H27 H H — — — —270 Ir 3 0 Ph Iq2 — — — — — — H H C7H15O H — — — — 271 Ir 3 0 Ph Iq2 — —— — — — H C15H31 H H — — — — 272 Ir 3 0 Ph Iq2 — — — — — — F F F F — — —— 273 Ir 3 0 Ph Iq2 — — — — — — H CF3O H H — — — — 274 Ir 3 0 Ph Iq2 — —— — — — H C3H7O H H — — — — 275 Ir 3 0 Ph Iq2 — — — — — — H C4H9O H H —— — — 276 Ir 2 1 Ph Iq2 Ph Pr — — — — H C18H37 H H H H H H 277 Ir 3 0 PhIq2 — — — — — — H C19H39 H H — — — — 278 Ir 2 1 Ph Iq2 — — C(CH3)3C(CH3)3 H — H C19H39 H H — — — — 279 Ir 3 0 Ph Iq2 — — — — — — H C20H41H H — — — — 280 Ir 2 1 Ph Iq2 — — — — — Pr H C20H41 H H — — — — 281 Ir 21 Ph Iq2 Ph Iq2 — — — — H CH3 H H H H H H 282 Ir 2 1 Ph Iq2 Ph Iq2 — — —— H C2H5 H H H H H H 283 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C3H7 H H H H H H284 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C4H9 H H H H H H 285 Ir 2 1 Ph Iq2 PhIq2 — — — — H C(CH3)3 H H H H H H 286 Ir 2 1 Ph Iq2 Ph Iq2 — — — — HC5H11 H H H H H H 287 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C6H13 H H H H H H288 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C7H15 H H H H H H 289 Ir 2 1 Ph Iq2Ph Iq2 — — — — H C8H17 H H H H H H 290 Ir 2 1 Ph Iq2 Ph Iq2 — — — — HC9H19 H H H H H H 291 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C10H21 H H H H H H292 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C11H23 H H H H H H 293 Ir 2 1 Ph Iq2Ph Iq2 — — — — H C12H25 H H H H H H 294 Ir 2 1 Ph Iq2 Ph Iq2 — — — — HC15H31 H H H F H H 295 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C18H37 H H H H CF3H 296 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C20H41 H H H H H H 297 Ir 2 1 PhIq2 Ph Iq2 — — — — H H H H H CH3 H H 298 Ir 2 1 Ph Iq2 Ph Iq2 — — — — HH H H H C2H5 H H 299 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H C3H7 H H 300Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H C4H9 H H B B′ B″ No R5 R6 R7 R8R9 R10 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 261 H H H H H H H H H H — — — — —— 262 H H H H H H — — — — — — — — — — 263 H H H H F H — — — — — — — — —— 264 H H H H CF3 H — — — — — — — — — — 265 H H H F H H — — — — — — — —— — 266 H H H CF3 H H — — — — — — — — — — 267 H H H H H H — — — — — — —— — — 268 H H H H CF3 H — — — — — — — — — — 269 H H H H H H — — — — — —— — — — 270 H H H H H H — — — — — — — — — — 271 H H H H H H — — — — — —— — — — 272 H H H CF3 H H — — — — — — — — — — 273 H H H H H H — — — — —— — — — — 274 H H H H H H — — — — — — — — — — 275 H H H H H H — — — — —— — — — — 276 H H H H H H H H H H — — — — — — 277 H H H H H H — — — — —— — — — — 278 H H H H H H — — — — — — — — — — 279 H H H H H H — — — — —— — — — — 280 H H H H H H — — — — — — H H H H 281 H H H H H H H H H H HH — — — — 282 H H H H H H H H H H H H — — — — 283 H H H H H H H H H H HH — — — — 284 H H H H H H H H H H H H — — — — 285 H H H H H H H H H H HH — — — — 286 H H H H H H H H H H H H — — — — 287 H H H H H H H H H H HH — — — — 288 H H H H H H H H H H H H — — — — 289 H H H H H H H H H H HH — — — — 290 H H H H H H H H H H H H — — — — 291 H H H H H H H H H H HH — — — — 292 H H H H H H H H H H H H — — — — 293 H H H F H H H H H H HH — — — — 294 H H H H H H H H H H H H — — — — 295 H H H H H H H H H H HH — — — — 296 H H H —C≡CC4H9 H H H H H H H H — — — — 297 H H H H H H — —— — — — — — — — 298 H H H H H H — — — — — — — — — — 299 H H H H H H — —— — — — — — — — 300 H H H H H H — — — — — — — — — —

TABLE 10 A A′ No M m n A B A′ B′ R1 R2 R3 R4 R1 R2 R3 R4 301 Ir 2 1 PhIq2 Ph Iq2 H H H H H C(CH3)3 H H 302 Ir 2 1 Ph Iq2 Ph Iq2 H H H H HC5H11 H H 303 Ir 2 1 Ph Iq2 Ph Iq2 H H H H H C6H13 H H 304 Ir 2 1 Ph Iq2Ph Iq2 H H H H H C7H15 H H 305 Ir 2 1 Ph Iq2 Ph Iq2 H H H H H C8H17 H H306 Ir 2 1 Ph Iq2 Ph Iq2 H CH2OC5H11 H H H C9H19 H H 307 Ir 2 1 Ph Iq2Ph Iq2 H H H H H C10H21 H H 308 Ir 2 1 Ph Iq2 Ph Iq2 H H H H H C11H23 HH 309 Ir 2 1 Ph Iq2 Ph Iq2 H H H H H C12H25 H H 310 Ir 2 1 Ph Iq2 Ph Iq2H H H H H C15H31 H H 311 Ir 2 1 Ph Iq2 Ph Iq2 H H H H H C18H37 H H 312Ir 2 1 Ph Iq2 Ph Iq2 H H H H H C20H41 H H 313 Ir 3 0 Ph Iq2 — — H H CH3H — — — — 314 Ir 3 0 Ph Iq2 — — H H C2H5 H — — — — 315 Ir 3 0 Ph Iq2 — —H H CH(CH3)2 H — — — — 316 Ir 3 0 Ph Iq2 — — H H C4H9 H — — — — 317 Ir 30 Ph Iq2 — — H H C(CH3)3 H — — — — 318 Ir 3 0 Ph Iq2 — — H H C5H11 H — —— — 319 Ir 3 0 Ph Iq2 — — H H C6H13 H — — — — 320 Ir 3 0 Ph Iq2 — — H HC7H15 H — — — — 321 Ir 3 0 Ph Iq2 — — H H C8H17 H — — — — 322 Ir 3 0 PhIq2 — — H H C9H19 H — — — — 323 Ir 3 0 Ph Iq2 — — H H C10H21 H — — — —324 Ir 3 0 Ph Iq2 — — H H C11H23 H — — — — 325 Ir 3 0 Ph Iq2 — — H HC12H25 H — — — — 326 Ir 3 0 Ph Iq2 — — H H C15H31 H — — — — 327 Ir 3 0Ph Iq2 — — H H C18H37 H — — — — 328 Ir 3 0 Ph Iq2 — — H H C20H41 H — — —— 329 Ir 2 1 Ph Iq2 Ph Iq2 H H CH3 H H H H H 330 Ir 2 1 Ph Iq2 Ph Iq2 HH C2H5 H H H H H 331 Ir 2 1 Ph Iq2 Ph Iq2 H H C3H7 H H H H H 332 Ir 2 1Ph Iq2 Ph Iq2 H H C4H9 H H H H H 333 Ir 2 1 Ph Iq2 Ph Iq2 H H C(CH3)3 HH H H H 334 Ir 2 1 Ph Iq2 Ph Iq2 H H C5H11 H H H H H 335 Ir 3 0 Ph Iq2Ph Iq2 H H C6H13 H H H H H 336 Ir 2 1 Ph Iq2 Ph Iq2 H H C7H15 H H H H H337 Ir 2 1 Ph Iq2 Ph Iq2 H H C8H17 H H H H H 338 Ir 2 1 Ph Iq2 Ph Iq2 HH C9H19 H H H H H 339 Ir 2 1 Ph Iq2 Ph Iq2 H H C10H21 H H H H H 340 Ir 21 Ph Iq2 Ph Iq2 H H C11H23 H H H H H B B′ No R5 R6 R7 R8 R9 R10 R5 R6 R7R8 R9 R10 301 H H H H H H H H H H H H 302 H H H H H H H H H H H H 303 HH H H H H H H H H H H 304 H H H H H H H H H H H H 305 H H H H H H H H HH H H 306 H H H H H H H H H H H H 307 H H H H H H H H H H H H 308 H H HH H H H H H H H H 309 H H H H H H H H H H H H 310 H H H —CH═CH—CH3 H H HH H H H H 311 H H H H H H H H H H H H 312 H H H H H H H H H H H H 313 HH H H H H — — — — — — 314 H H H H H H — — — — — — 315 H H H H H H — — —— — — 316 H H H H H H — — — — — — 317 H H H H H H — — — — — — 318 H H HH H H — — — — — — 319 H H H H H H — — — — — — 320 H H H H H H — — — — —— 321 H H H H H H — — — — — — 322 H H H H H H — — — — — — 323 H H H H HH — — — — — — 324 H H H H H H — — — — — — 325 H H H H H H — — — — — —326 H H H COOC6H13 H H — — — — — — 327 H H H H H H — — — — — — 328 H H HOCH2C3F7 H H — — — — — — 329 H H H H H H H H H H H H 330 H H H H H H H HH H H H 331 H H H H H H H H H H H H 332 H H H H H H H H H H H H 333 H HH H H H H H H H H H 334 H H H H H H H H H H H H 335 H H H H H H H H H HH H 336 H H H H H H H H H H H H 337 H H H H H H H H H H H H 338 H H H HH H H H H H H H 339 H H H H H H H H H H H H 340 H H H H H H H H H H H H

TABLE 11-1 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 R3 R4 341Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H C12H25 H H H H H 342 Ir 2 1 Ph Iq2 PhIq2 — — — — H H C15H31 H H H H H 343 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H HC18H37 H H H H H 344 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H C20H41 H H H H H345 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H H CH3 H 346 Ir 2 1 Ph Iq2 PhIq2 — — — — H H H H H H C2H5 H 347 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H HH H C3H7 H 348 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H H C4H9 H 349 Ir 21 Ph Iq2 Ph Iq2 — — — — H H H H H H C(CH3)3 H 350 Ir 2 1 Ph Iq2 Ph Iq2 —— — — H H H H H H C5H11 H 351 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H HC6H13 H 352 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H H C7H15 H 353 Ir 2 1Ph Iq2 Ph Iq2 — — — — H H H H H H C8H17 H 354 Ir 2 1 Ph Iq2 Ph Iq2 — — —— H H H H H H C9H19 H 355 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H HC10H21 H 356 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H COCH3 H H H C11H23 H 357Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H H C12H25 H 358 Ir 2 1 Ph Iq2 PhIq2 — — — — H H C7H15O H H H C15H31 H 359 Ir 2 1 Ph Iq2 Ph Iq2 — — — — HH H H H H C18H37 H 360 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H CN H H H C20H41H 361 Ir 3 0 Ph Iq2 — — — — — — H

H H — — — — 362 Ir 3 0 Ph Iq2 — — — — — — H

H H — — — — 363 Ir 3 0 Ph Iq2 — — — — — — H

H H — — — — 364 Ir 2 1 Ph Iq2 Ph Pr — — — — H

H H H H H H 365 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H

H H — — — — 366 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — H

H H — — — — 367 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H

H H — — — — 368 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H

H H — — — — 369 Ir 2 1 Ph Iq2 — — — — — Pr H

H H — — — — 370 Ir 2 1 Ph Iq2 — — — — — Pr H

H H — — — — 371 Ir 2 1 Ph Iq2 — — — — — Iq2 H

H H — — — — 372 Ir 3 0 Ph Iq2 — — — — — — H CH3O H H — — — — 373 Ir 3 0Ph Iq2 — — — — — — H CH3O H H H H H H 374 Ir 2 1 Ph Iq2 Ph Pr — — — — HCH3O H H — — — — 375 Ir 3 0 Ph Iq2 — — — — — — H H CH3O H — — — — 376 Ir2 1 Ph Iq2 — — CH3 CH3 CH3 — H CH3O H H — — — — 377 Ir 2 1 Ph Iq2 — —C(CH3)3 C(CH3)3 H — H CH3O H H — — — — 378 Ir 2 1 Ph Iq2 — — CH3 C4H9CH3 — H CH3O H H — — — — 379 Ir 2 1 Ph Iq2 — — — — — Pr H CH3O H H — — —— 380 Ir 2 1 Ph Iq2 — — — — — Pr H CH3O H H — — — — B B′ B″ R5 R6 R7 R8R9 R10 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R9 R10 H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — —— — — — H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H H HH H — — H H H H H H H H H H H H H H C4H9 H — — H H H H H H — — — — — — HH H H H H H H H F H H — — — — — — — — — — — — H H H H C6H13 H — — — — —— — — — — — — H H H H H H H H H H — — — — — — — — H H H H H H — — — — —— — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — — — — —— — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — — — — —— — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — — — — —— — — — — — — H H H F H H — — — — — — — — — — — — H H H H C6H13 H — — —— — — — — — — — — H H H H H H H H H H — — — — — — — — H H H H H H — — —— — — — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — — —— — — — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — — —— — — H H H H — — H H H H H H — — — — — — H H C4H9 H — —

TABLE 12 A A′ No M m n A B A B E G J B R1 R2 R3 R4 R1 R2 R3 R4 381 Ir 21 Ph Iq2 — — — — — Iq2 H CH3O H H — — — — 382 Ir 3 0 Ph Iq2 — — — — — —H C2H5O H H — — — — 383 Ir 3 0 Ph Iq2 — — — — — — H C2H5O H H — — — —384 Ir 3 0 Ph Iq2 — — — — — — H C2H5O H H — — — — 385 Ir 2 1 Ph Iq2 PhPr — — — — H C2H5O H H H H H H 386 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H C2H5OH H — — — — 387 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — H C2H5O H H — — — — 388Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H C2H5O H H — — — — 389 Ir 2 1 PhIq2 — — CH3 C4H9 CH3 — H C2H5O H H — — — — 390 Ir 2 1 Ph Iq2 — — — — —Pr H C2H5O H H — — — — 391 Ir 2 1 Ph Iq2 — — — — — Pr H C2H5O H H — — —— 392 Ir 2 1 Ph Iq2 — — — — — Iq2 H C2H5O H H — — — — 393 Ir 3 0 Ph Iq2— — — — — — H C6H13O H H — — — — 394 Ir 3 0 Ph Iq2 — — — — — — H C6H13OH H — — — — 395 Ir 2 1 Ph Iq2 Ph Pr — — — — H C6H13O H H H H H H 396 Ir2 1 Ph Iq2 — — CH3 CH3 H — H C6H13O H H — — — — 397 Ir 2 1 Ph Iq2 — —CH3 CH3 CH3 — H C6H13O H H — — — — 399 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 —H C6H13O H H — — — — 400 Ir 2 1 Ph Iq2 — — — — — Pr H C6H13O H H — — — —401 Ir 2 1 Ph Iq2 — — — — — Pr H C6H13O H H — — — — 402 Ir 2 1 Ph Iq2 —— — — — Iq2 H C6H13O H H — — — — 403 Ir 3 0 Ph Iq2 — — — — — — H C7H15OH H — — — — 404 Ir 3 0 Ph Iq2 — — — — — — H C7H15O H H — — — — 405 Ir 30 Ph Iq2 — — — — — — H C7H15O H H — — — — 406 Ir 3 0 Ph Iq2 — — — — — —H (CH3)3CO H H — — — — 407 Ir 3 0 Ph Iq2 — — — — — — H C5H11O H H — — —— 408 Ir 3 0 Ph Iq2 — — — — — — H CF3O H H — — — — 409 Ir 3 0 Ph Iq2 — —— — — — H CF3O H H — — — — 410 Ir 3 0 Ph Iq2 — — — — — — H CF3O H H — —— — 411 Ir 3 0 Ph Iq2 — — — — — — H CF3O H H — — — — 412 Ir 3 0 Ph Iq2 —— — — — — H C7H15O H H — — — — 413 Ir 2 1 Ph Iq2 — — — — — Iq2 H C7H15OH H — — — — 414 Ir 3 0 Ph Iq2 — — — — — — H (C4H9)3Si H H — — — — 415 Ir3 0 Ph Iq2 — — — — — — H C12H25O H H — — — — 416 Ir 3 0 Ph Iq2 — — — — —— H C12H25O H H — — — — 417 Ir 2 1 Ph Iq2 Ph Pr — — — — H C12H25O H H HH H H 418 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H (CH3)3Si H H — — — — 419 Ir 21 Ph Iq2 — — — — — Pr H C18H37O H H — — — — 420 Ir 2 1 Ph Iq2 — — — — —Iq2 H C18H37O H H — — — — B B′ B″ No R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R5R6 R7 R8 R9 R10 381 H H H H H H — — — — H H H H H H 382 H H H H H H — —— — — — — — — — 383 H H H F H H — — — — — — — — — — 384 H H H H C6H13 H— — — — — — — — — — 385 H H H H H H H H H H — — — — — — 386 H H H H H H— — — — — — — — — — 387 H H H H H H — — — — — — — — — — 388 H H H H H H— — — — — — — — — — 389 H H H H H H — — — — — — — — — — 390 H H H H H H— — — — H H H H — — 391 H H H H H H — — — — H H C4H9 H — — 392 H H H H HH — — — — H H H H H H 393 H H H F H H — — — — — — — — — — 394 H H H HC6H13 H — — — — — — — — — — 395 H H H H H H H H H H — — — — — — 396 H HH H H H — — — — — — — — — — 397 H H H H H H — — — — — — — — — — 399 H HH H H H — — — — — — — — — — 400 H H H H H H — — — — H H H H — — 401 H HH H H H — — — — H H C4H9 H — — 402 H H H H H H — — — — H H H H H H 403 HH H H H H — — — — — — — — — — 404 H H H F H H — — — — — — — — — — 405 HH H H C6H13 H — — — — — — — — — — 406 H H H H H H — — — — — — — — — —407 H H H H H H — — — — — — — — — — 408 H H H F H H — — — — — — — — — —409 H H H H F H — — — — — — — — — — 410 H H H CF3 H H — — — — — — — — —— 411 H H H H CF3 H — — — — — — — — — — 412 H H H F H H — — — — — — — —— — 413 H H H H H H — — — — H H H H H H 414 H H H H H H — — — — — — — —— — 415 H H H F H H — — — — — — — — — — 416 H H H H C6H13 H — — — — — —— — — — 417 H H H H H H H H H H — — — — — — 418 H H H H H H — — — — — —— — — — 419 H H H H H H — — — — H H C4H9 H — — 420 H H H H H H — — — — HH H H H H

TABLE 13 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 R3 R4 421 Ir3 0 Ph Iq2 — — — — — — F H F H — — — — 422 Ir 3 0 Ph Iq2 — — — — — — F HF H — — — — 423 Ir 3 0 Ph Iq2 — — — — — — F H F H — — — — 424 Ir 2 1 PhIq2 Ph Pr — — — — F H F H H H H H 425 Ir 2 1 Ph Iq2 — — CH3 CH3 H — F HF H — — — — 426 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — F H F H — — — — 427 Ir 21 Ph Iq2 — — C(CH3)3 C(CH3)3 H — F H F H — — — — 428 Ir 2 1 Ph Iq2 — —CH3 C4H9 CH3 — F H F H — — — — 429 Ir 2 1 Ph Iq2 — — — — — Pr F H F H —— — — 430 Ir 2 1 Ph Iq2 — — — — — Pr F H F H — — — — 431 Ir 2 1 Ph Iq2 —— — — — Iq2 F H F H — — — — 432 Ir 3 0 Ph Iq2 — — — — — — H F H F — — —— 433 Ir 3 0 Ph Iq2 — — — — — — H F H F — — — — 434 Ir 3 0 Ph Iq2 — — —— — — H F H F — — — — 435 Ir 2 1 Ph Iq2 Ph Pr — — — — H F H F H H H H436 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H F H F — — — — 437 Ir 2 1 Ph Iq2 — —CH3 CH3 CH3 — H F H F — — — — 438 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H —H F H F — — — — 439 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H F H F — — — — 440Ir 2 1 Ph Iq2 — — — — — Pr H F H F — — — — 441 Ir 2 1 Ph Iq2 — — — — —Pr H F H F — — — — 442 Ir 2 1 Ph Iq2 — — — — — Iq2 H F H F — — — — 443Ir 3 0 Ph Iq2 — — — — — — F F F F — — — — 444 Ir 3 0 Ph Iq2 — — — — — —F F F F — — — — 445 Ir 3 0 Ph Iq2 — — — — — — F F F F — — — — 446 Ir 2 1Ph Iq2 Ph Pr — — — — F F F F H H H H 447 Ir 2 1 Ph Iq2 — — CH3 CH3 H — FF F F — — — — 448 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — F F F F — — — — 449 Ir2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — F F F F — — — — 450 Ir 2 1 Ph Iq2 — —CH3 C4H9 CH3 — F F F F — — — — 451 Ir 2 1 Ph Iq2 — — — — — Pr F F F F —— — — 452 Ir 2 1 Ph Iq2 — — — — — Pr F F F F — — — — 453 Ir 2 1 Ph Iq2 —— — — — Iq2 F F F F — — — — 454 Ir 3 0 Ph Iq2 — — — — — — F F F F — — —— 455 Ir 3 0 Ph Iq2 — — — — — — F F F F — — — — 456 Ir 2 1 Ph Iq2 Ph Pr— — — — F F F F H H H H 457 Ir 2 1 Ph Iq2 — — CH3 CH3 H — F F F F — — —— 458 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — F F F F — — — — 459 Ir 2 1 Ph Iq2— — C(CH3)3 C(CH3)3 H — F F F F — — — — B B′ B″ No R5 R6 R7 R8 R9 R10 R5R6 R7 R8 R5 R6 R7 R8 R9 R10 421 H H H H H H — — — — — — — — — — 422 H HH F H H — — — — — — — — — — 423 H H H H C6H13 H — — — — — — — — — — 424H H H H H H H H H H — — — — — — 425 H H H H H H — — — — — — — — — — 426H H H H H H — — — — — — — — — — 427 H H H H H H — — — — — — — — — — 428H H H H H H — — — — — — — — — — 429 H H H H H H — — — — H H H H — — 430H H H H H H — — — — H H C4H9 H — — 431 H H H H F H — — — — H H H H H H432 H H H H F H — — — — — — — — — — 433 H H H F F H — — — — — — — — — —434 H H H H C6H13 H — — — — — — — — — — 435 H H H H H H H H H H — — — —— — 436 H H H H H H — — — — — — — — — — 437 H H H H H H — — — — — — — —— — 438 H H H H H H — — — — — — — — — — 439 H H H H H H — — — — — — — —— — 440 H H H H H H — — — — H H H H — — 441 H H H H H H — — — — H H C4H9H — — 442 H H H H H H — — — — H H H H H H 443 H H H H H H — — — — — — —— — — 444 H H H F H H — — — — — — — — — — 445 H H H H C6H13 H — — — — —— — — — — 446 H H H H H H H H H H — — — — — — 447 H H H H H H — — — — —— — — — — 448 H H H H H H — — — — — — — — — — 449 H H H H H H — — — — —— — — — — 450 H H H H H H — — — — — — — — — — 451 H H H H H H — — — — HH H H — — 452 H H H H H H — — — — H H C4H9 H — — 453 H H H H H H — — — —H H H H H H 454 F F F F F F — — — — — — — — — — 455 F F F F C6H13 F — —— — — — — — — — 456 F F F F F F H H H H — — — — — — 457 F F F F F F — —— — — — — — — — 458 F F F F F F — — — — — — — — — — 459 F F F F F F — —— — — — — — — —

TABLE 14-1A A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 R3 R4 460Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — F F F F — — — — 461 Ir 2 1 Ph Iq2 — — —— — Pr F F F F — — — — 462 Ir 2 1 Ph Iq2 — — — — — Pr F F F F — — — —463 Ir 2 1 Ph Iq2 — — — — — Iq2 F F F F — — — — 464 Ir 3 0 Ph Iq2 — — —— — — H C2F5 H H — — — — 465 Ir 3 0 Ph Iq2 — — — — — — H C2F5 H H — — —— 466 Ir 3 0 Ph Iq2 — — — — — — H C3F7 H H — — — — 467 Ir 2 1 Ph Iq2 PhPr — — — — H C3F7 H H H H H H 468 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H C4F9 HH — — — — 469 Ir 3 0 Ph Iq2 — — — — — — H C3F7CH2CH2O H H — — — — 470 Ir2 1 Ph Iq2 Ph Iq2 — — — — H C3F7CH2CH2O H H H H H H 471 Ir 1 2 Ph Iq2 PhIq2 — — — — H C3F7CH2CH2O H H H H H H 472 Ir 2 1 Ph Iq2 — — — — — Pr HC5F11 H H — — — — 473 Ir 2 1 Ph Iq2 — — — — — Pr H C2F5 H H — — — — 474Ir 2 1 Ph Iq2 — — — — — Iq2 H C3F7 H H — — — — 475 Ir 3 0 Ph Iq2 — — — —— — H C6F13 H H — — — — 476 Ir 3 0 Ph Iq2 — — — — — — H C6F13 H H — — —— 477 Ir 3 0 Ph Iq2 — — — — — — H C6F13 H H — — — — 478 Ir 3 0 Ph Iq2 —— — — — — H C6F13 H H — — — — 479 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H C6F13 HH H H H H 480 Ir 2 1 Ph Iq2 Ph Iq2 — — — — H H H H H C6F13 H H 481 Ir 30 Ph Iq2 — — — — — — H C6F13CH2O H H — — — — 482 Ir 2 1 Ph Iq2 — — CH3C4H9 CH3 — H C18F37 H H — — — — 483 Ir 2 1 Ph Iq2 Ph Iq2 — — — — HC6F13CH2O H H H H H H 484 Ir 1 2 Ph Iq2 Ph Iq2 — — — — H C6F13CH2O H H HH H H 485 Ir 2 1 Ph Iq2 — — — — — Iq2 H C20F41 H H — — — — 486 Ir 3 0 PhIq2 — — — — — — H

H H — — — — 487 Ir 3 0 Ph Iq2 — — — — — — H

H H — — — — 488 Ir 3 0 Ph Iq2 — — — — — — H

H H — — — — 489 Ir 2 1 Ph Iq2 Ph Pr — — — — H

H H H H H H 490 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H

H H — — — — 491 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — H

H H — — — — 492 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H

H H — — — — 493 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H

H H — — — — 494 Ir 2 1 Ph Iq2 — — — — — Pr H

H H — — — — 495 Ir 2 1 Ph Iq2 — — — — — Pr H

H H — — — — 496 Ir 2 1 Ph Iq2 — — — — — Iq2 H

CH3 H — — — — 497 Ir 3 0 Ph Iq2 — — — — — — H H F F — — — — 498 Ir 3 0Ph Iq2 — — — — — — H H F F — — — — 499 Ir 3 0 Ph Iq2 — — — — — — H H F F— — — — 500 Ir 2 1 Ph Iq2 Ph Pr — — — — H H F F H H H H 501 Ir 2 1 PhIq2 — — CH3 CH3 H — H H F F — — — — 502 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 —H H F F — — — — 503 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H H F F — — —— 504 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H H F F — — — — 505 Ir 2 1 Ph Iq2— — — — — Pr H H F F — — — — 506 Ir 2 1 Ph Iq2 — — — — — Pr H H F F — —— — 507 Ir 2 1 Ph Iq2 — — — — — Iq2 H H F F — — — — 508 Ir 3 0 Ph Iq2 —— — — — — H CH3 F F — — — — 509 Ir 3 0 Ph Iq2 — — — — — — H CH3 F F — —— — B B′ B″ R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R9 R10 F FF F F F — — — — — — — — — — — — F F F F F F — — — — — — H H H H — — F FF F F F — — — — — — H H C4H9 H — — F F F F F F — — — — — — H H H H H H HH H H H H — — — — — — — — — — — — H H H F H H — — — — — — — — — — — — HH H H C6H13 H — — — — — — — — — — — — H H H H H H H H H H — — — — — — —— H H H H H H — — — — — — — — — — — — H H H H H H — — — — — — — — — — —— H H H H H H H H H H H H — — — — — — H H H H H H H H H H H H — — — — —— H H H H H H — — — — — — H CH3 H H — — H H H H H H — — — — — — H H C4H9H — — H H H H H H — — — — — — H H H H H H H H H H H H — — — — 13 — — — —— — — H H H CF3 H H — — — — — — — — — — — — H H H H CF3 H — — — — — — —— — — — — H H H H F H — — — — — — — — — — — — H H H H F H H H H H H H —— — — — — H H H H H H H H H H H H — — — — — — H H H H H H — — — — — — HH H H H H H H H H H H — — — — — — — — — — — — H H H H H H H H H H H H —— — — — — H H H H H H H H H H H H — — — — — — H H H H H H — — — — — — —— — — — — H H H H H H — — — — — — — — — — — — H H H F H H — — — — — — —— — — — — H H H H C6H13 H — — — — — — — — — — — — H H H H H H H H H H —— — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — — — — —— — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — — — — —— — — — — — — H H H H H H — — — — — — H H H H — — H H H H H H — — — — —— H H C2H5 H — — H H H H H H — — — — — — H H H H H H H H H H H H — — — —— — — — — — — — H H H F H H — — — — — — — — — — — — H H H H C6H13 H — —— — — — — — — — — — H H H H H H H H H H — — — — — — — — H H H H H H — —— — — — — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — —— — — — — — — — — — H H H H H H — — — — — — — — — — — — H H H H H H — —— — — — H H H H — — H H H H H H — — — — — — H H C4H9 H — — H H H H H H —— — — — — H H H H H H H H H CF3 H H — — — — — — — — — — — — H H H F H H— — — — — — — — — — — —

TABLE 15 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 510 Ir 3 0Ph Iq2 — — — — — — H CH3 F F — — 511 Ir 2 1 Ph Iq2 Ph Pr — — — — H CH3 FF H H 512 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H CH3 F F — — 513 Ir 2 1 Ph Iq2— — CH3 CH3 CH3 — H CH3 F F — — 514 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H— H CH3 F F — — 515 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H CH3 F F — — 516Ir 2 1 Ph Iq2 — — — — — Pr H CH3 F F — — 517 Ir 2 1 Ph Iq2 — — — — — PrH CH3 F F — — 518 Ir 2 1 Ph Iq2 — — — — — Iq2 H CH3 F F — — 519 Ir 3 0Ph Iq2 — — — — — — H C2H5 F F — — 520 Ir 3 0 Ph Iq2 — — — — — — H C2H5 FF — — 521 Ir 3 0 Ph Iq2 — — — — — — H C2H5 F F — — 522 Ir 2 1 Ph Iq2 PhPr — — — — H C2H5 F F H H 523 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H C2H5 F F —— 524 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — H C2H5 F F — — 525 Ir 2 1 Ph Iq2 —— C(CH3)3 C(CH3)3 H — H C2H5 F F — — 526 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3— H C3H7 F F — — 527 Ir 2 1 Ph Iq2 — — — — — Pr H C3H7 F F — — 528 Ir 21 Ph Iq2 — — — — — Pr H C3H7 F F — — 529 Ir 2 1 Ph Iq2 — — — — — Iq2 HC3H7 F F — — 530 Ir 3 0 Ph Iq2 — — — — — — H C4H9 F F — — 531 Ir 3 0 PhIq2 — — — — — — H C4H9 F F — — 532 Ir 3 0 Ph Iq2 — — — — — — H C4H9 F F— — 533 Ir 2 1 Ph Iq2 Ph Pr — — — — H C4H9 F F H H 534 Ir 2 1 Ph Iq2 — —CH3 CH3 H — H C4H9 F F — — 535 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — H C4H9 FF — — 536 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H C4H9 F F — — 537 Ir 21 Ph Iq2 — — CH3 C4H9 CH3 — H C4H9 F F — — 538 Ir 2 1 Ph Iq2 — — — — —Pr H C4H9 F F — — 539 Ir 2 1 Ph Iq2 — — — — — Pr H C4H9 F F — — 540 Ir 21 Ph Iq2 — — — — — Iq2 H C4H9 F F — — 541 Ir 3 0 Ph Iq2 — — — — — — HC(CH3)3 F F — — 542 Ir 3 0 Ph Iq2 — — — — — — H C(CH3)3 F F — — 543 Ir 30 Ph Iq2 — — — — — — H C(CH3)3 F F — — 544 Ir 2 1 Ph Iq2 Ph Pr — — — — HC(CH3)3 F F H H 545 Ir 2 1 Ph Iq2 — — CH3 CH3 F — H C5H11 F F — — 546 Ir2 1 Ph Iq2 — — CH3 CH3 CH3 — H C5H11 F F — — 547 Ir 2 1 Ph Iq2 — —C(CH3)3 C(CH3)3 H — H C5H11 F F — — 548 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 —H C5H11 F F — — 549 Ir 2 1 Ph Iq2 — — — — — Pr H C5H11 F F — — A′ B B′B″ No R3 R4 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R5 R6 R7 R8 R9 R10 510 — — HH H H C6H13 H — — — — — — — — — — 511 H H H H H H H H H H H H — — — — —— 512 — — H H H H H H — — — — — — — — — — 513 — — H H H H H H — — — — —— — — — — 514 — — H H H H H H — — — — — — — — — — 515 — — H H H H H H —— — — — — — — — — 516 — — H H H H H H — — — — H H H H — — 517 — — H H HH H H — — — — H H C4H9 H — — 518 — — H H H H H H — — — — H H H H H H 519— — H H H H H H — — — — — — — — — — 520 — — H H H F H H — — — — — — — —— — 521 — — H H H H C6H13 H — — — — — — — — — — 522 H H H H H H H H H HH H — — — — — — 523 — — H H H H H H — — — — — — — — — — 524 — — H H H HH H — — — — — — — — — — 525 — — H H H H H H — — — — — — — — — — 526 — —H H H H H H — — — — — — — — — — 527 — — H H H H H H — — — — H H H H — —528 — — H H H H H H — — — — H H C4H9 H — — 529 — — H H H H H H — — — — HH H H H H 530 — — H H H H H H — — — — — — — — — — 531 — — H H H F H H —— — — — — — — — — 532 — — H H H H C6H13 H — — — — — — — — — — 533 H H HH H H H H H H H H — — — — — — 534 — — H H H H H H — — — — — — — — — —535 — — H H H H H H — — — — — — — — — — 536 — — H H H H H H — — — — — —— — — — 537 — — H H H H H H — — — — — — — — — — 538 — — H H H H H H — —— — H H H H — — 539 — — H H H H H H — — — — H H CH3 H — — 540 — — H H HH H H — — — — H H H H H H 541 — — H H H CF3 H H — — — — — — — — — — 542— — H H H F H H — — — — — — — — — — 543 — — H H H H C6H13 H — — — — — —— — — — 544 H H H H H H H H H H H H — — — — — — 545 — — H H H H H H — —— — — — — — — — 546 — — H H H H H H — — — — — — — — — — 547 — — H H H HH H — — — — — — — — — — 548 — — H H H H H H — — — — — — — — — — 549 — —H H H H H H — — — — H H H H — —

TABLE 16 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 550 Ir 2 1Ph Iq2 — — — — — Pr H C6H13 F F — — 551 Ir 2 1 Ph Iq2 — — — — — Iq2 HC6H13 F F — — 552 Ir 3 0 Ph Iq2 — — — — — — H C6H13 F F — — 553 Ir 3 0Ph Iq2 — — — — — — H C6H13 F F — — 554 Ir 3 0 Ph Iq2 — — — — — — H C6H13F F — — 555 Ir 2 1 Ph Iq2 Ph Pr — — — — H C6H13 F F H H 556 Ir 2 1 PhIq2 — — CF3 CF3 H — H C6H13 F F — — 557 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 —H C6H13 F F — — 558 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H — H C7H15 F F —— 559 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H C7H15 F F — — 560 Ir 2 1 Ph Iq2— — — — — Pr H C7H15 F F — — 561 Ir 2 1 Ph Iq2 — — — — — Pr H C8H17 F F— — 562 Ir 2 1 Ph Iq2 — — — — — Iq2 H C8H17 F F — — 563 Ir 3 0 Ph Iq2 —— — — — — H C8H17 F F — — 564 Ir 3 0 Ph Iq2 — — — — — — H C9H19 F F — —565 Ir 3 0 Ph Iq2 — — — — — — H C9H19 F F — — 566 Ir 2 1 Ph Iq2 Ph Pr —— — — H C10H21 F F H H 567 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H C10H21 F F —— 568 Ir 2 1 Ph Iq2 — — CH3 CH3 CH3 — H C11H23 F F — — 569 Ir 2 1 Ph Iq2— — C(CH3)3 C(CH3)3 H — H C12H25 F F — — 570 Ir 2 1 Ph Iq2 — — CH3 C4H9CH3 — H C13H27 F F — — 571 Ir 2 1 Ph Iq2 — — — — — Pr H C14H29 F F — —572 Ir 2 1 Ph Iq2 — — — — — Pr H C15H31 F F — — 573 Ir 2 1 Ph Iq2 — — —— — Iq2 H C15H31 F F — — 574 Ir 3 0 Ph Iq2 — — — — — — H C16H33 F F — —575 Ir 3 0 Ph Iq2 — — — — — — H C17H35 F F — — 576 Ir 3 0 Ph Iq2 — — — —— — H C17H35 F F — — 577 Ir 2 1 Ph Iq2 Ph Pr — — — — H C17H35 F F H H578 Ir 2 1 Ph Iq2 — — CH3 CH3 H — H C17H35 F F — — 579 Ir 2 1 Ph Iq2 — —CH3 CH3 CH3 — H C17H35 F F — — 580 Ir 2 1 Ph Iq2 — — C(CH3)3 C(CH3)3 H —H C18H37 F F — — 581 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — H C18H37 F F — —582 Ir 2 1 Ph Iq2 — — — — — Pr H C18H37 F F — — 583 Ir 2 1 Ph Iq2 — — —— — Pr H C19H39 F F — — 584 Ir 2 1 Ph Iq2 — — — — — Iq2 H C20H41 F F — —585 Ir 3 0 Ph Iq2 — — — — — — F F F H — — 586 Ir 3 0 Ph Iq2 — — — — — —F F F H — — 587 Ir 3 0 Ph Iq2 — — — — — — F F F H — — 588 Ir 2 1 Ph Iq2Ph Pr — — — — F F F H H H 589 Ir 2 1 Ph Iq2 — — CH3 CH3 H — F F F H — —A′ B B′ B″ No R3 R4 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R5 R6 R7 R8 R9 R10550 — — H H H H H H — — — — H H C4H9 H — — 551 — — H H H H H H — — — — HH H H H H 552 — — H H H H H H — — — — — — — — — — 553 — — H H H F H H —— — — — — — — — — 554 — — H H H H C6H13 H — — — — — — — — — — 555 H H HH H H H H H H H H — — — — — — 556 — — H H H H H H — — — — — — — — — —557 — — H H H H H H — — — — — — — — — — 558 — — H H H H H H — — — — — —— — — — 559 — — H H H H H H — — — — — — — — — — 560 — — H H H H H H — —— — H H H H — — 561 — — H H H H H H — — — — H H C4H9 H — — 562 — — H H HH H H — — — — H H H H H H 563 — — H H H H H H — — — — — — — — — — 564 —— H H H F H H — — — — — — — — — — 565 — — H H H H C6H13 H — — — — — — —— — — 566 H H H H H H H H H H H H — — — — — — 567 — — H H H H H H — — —— — — — — — — 568 — — H H H H H H — — — — — — — — — — 569 — — H H H H HH — — — — — — — — — — 570 — — H H H H H H — — — — — — — — — — 571 — — HH H H H H — — — — H H H H — — 572 — — H H H H H H — — — — H H C4H9 H — —573 — — H H H H H H — — — — H H H H H H 574 — — H H H H H H — — — — — —— — — — 575 — — H H H F H H — — — — — — — — — — 576 — — H H H H C6H13 H— — — — — — — — — — 577 H H H H H H H H H H H H — — — — — — 578 — — H HH H H H — — — — — — — — — — 579 — — H H H H H H — — — — — — — — — — 580— — H H H H H H — — — — — — — — — — 581 — — H H H H H H — — — — — — — —— — 582 — — H H H H H H — — — — H H H H — — 583 — — H H H H H H — — — —H H C2H5 H — — 584 — — H H H H H H — — — — H H H H H H 585 — — H H H H HH — — — — — — — — — — 586 — — H H H F H H — — — — — — — — — — 587 — — HH H H C6H13 H — — — — — — — — — — 588 H H H H H H H H H H H H — — — — —— 589 — — H H H H H H — — — — — — — — — —

TABLE 17 A A′ No M m n A B A′ B′ E G J B″ R1 R2 R3 R4 R1 R2 590 Ir 2 1Ph Iq2 — — CH3 CH3 CH3 — F F F H — — 591 Ir 2 1 Ph Iq2 — — C(CH3)3C(CH3)3 H — F F F H — — 592 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — F F F H — —593 Ir 2 1 Ph Iq2 — — — — — Pr F F F H — — 594 Ir 2 1 Ph Iq2 — — — — —Pr F F F H — — 595 Ir 2 1 Ph Iq2 — — — — — Iq2 F F F H — — 596 Ir 3 0 PhIq2 — — — — — — F H F H — — 597 Ir 3 0 Ph Iq2 — — — — — — F H F H — —598 Ir 3 0 Ph Iq2 — — — — — — F H F H — — 599 Ir 2 1 Ph Iq2 Ph Pr — — —— F H F H H H 600 Ir 2 1 Ph Iq2 — — CH3 CH3 H — F H F H — — 601 Ir 2 1Ph Iq2 — — CH3 CH3 CH3 — F H F H — — 602 Ir 2 1 Ph Iq2 — — C(CH3)3C(CH3)3 H — F H F H — — 603 Ir 2 1 Ph Iq2 — — CH3 C4H9 CH3 — F H F H — —604 Ir 2 1 Ph Iq2 — — — — — Pr F H F H — — 605 Ir 2 1 Ph Iq2 — — — — —Pr F H F H — — 606 Ir 2 1 Ph Iq2 — — — — — Iq2 F H F H — — 607 Ir 3 0 PhIq2 — — — — — — H CF3 H H — — 608 Ir 3 0 Ph Iq2 — — — — — — H F H H — —609 Ir 3 0 Ph Iq5 — — — — — — H H H H — — 610 Ir 3 0 Ph Iq5 — — — — — —H H H H — — 611 Ir 2 1 Ph Iq5 Ph Pr — — — — H H H H H H 612 Ir 2 1 PhIq5 — — CH3 CH3 H — H H H H — — 613 Ir 2 1 Ph Iq5 — — CH3 CH3 CH3 — H HH H — — 614 Ir 2 1 Ph Iq5 — — C(CH3)3 C(CH3)3 H — H H H H — — 615 Ir 2 1Ph Iq5 — — CH3 C4H9 CH3 — H H H H — — 616 Ir 2 1 Ph Iq5 — — — — — Pr H HH H — — 617 Ir 2 1 Ph Iq5 — — — — — Pr H H H H — — 618 Ir 2 1 Ph Iq5 — —— — — Iq2 H H H H H H 619 Ir 2 1 Ph Iq2 Ph Pi — — — — H H H H H H A′ BB′ B″ No R3 R4 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8 R5 R6 R7 R8 R9 R10 590 — —H H H H H H — — — — — — — — — — 591 — — H H H H H H — — — — — — — — — —592 — — H H H H H H — — — — — — — — — — 593 — — H H H H H H — — — — H HH H — — 594 — — H H H H H H — — — — H H C4H9 H — — 595 — — H H H H H H —— — — H H H H H H 596 — — H H H H CF3 H — — — — — — — — — — 597 — — H HH F CF3 H — — — — — — — — — — 598 — — H H H H CF3 H — — — — — — — — — —599 H H H H H H CF3 H H H H H — — — — — — 600 — — H H H H CF3 H — — — —— — — — — — 601 — — H H H H CF3 H — — — — — — — — — — 602 — — H H H HCF3 H — — — — — — — — — — 603 — — H H H H CF3 H — — — — — — — — — — 604— — H H H H CF3 H — — — — H H H H — — 605 — — H H H H CF3 H — — — — H HCH3 H — — 606 — — H H H H CF3 H — — — — H H H H H H 607 — — H H H H H H— — — — — — — — — — 608 — — H H H H H H — — — — — — — — — — 609 — — — HH H H H — — — — — — — — — — 610 — — — H H H H H — — — — — — — — — — 611H H — H H H H H H H H H — — — — — — 612 — — — H H H H H — — — — — — — —— — 613 — — — H H H H H — — — — — — — — — — 614 — — — H H H H H — — — —— — — — — — 615 — — — H H F H H — — — — — — — — — — 616 — — — H H H H H— — — — H H H H — — 617 — — — H H H H H — — — — H H CH3 H — — 618 H H —H H H H H — — — — H H H H H H 619 H H H H H H H H H H H — — — — — — —

TABLE 18 A A′ B No M m n A B A′ B′ B″ R1 R2 R3 R4 R1 R2 R3 R4 R5 620 Ir2 1 Ph Iq2 Ph Py1 — H H H H H H H H H 621 Ir 2 1 Ph Iq2 Ph Py2 — H H H HH H H H H 622 Ir 2 1 Ph Iq2 Ph Pz — H CF3 H H H H H H H 623 Ir 2 1 PhIq2 Ph Qn3 — H H H H H H H H H 624 Ir 2 1 Ph Iq2 Ph Xa — H H H H H H H HH 625 Ir 2 1 Ph Iq2 Ph Bz — H H H H H H H H H 626 Ir 2 1 Ph Iq2 Ph Bo —H H H H H H H H H 627 Ir 2 1 Ph Iq2 Ph Oz — H H H H H H H H H 628 Ir 2 1Ph Iq2 Ph Sz — H H H H H H H H H 629 Ir 2 1 Tn4 Iq2 Ph Pr — H H — — H HH H H 630 Ir 2 1 Ph Iq2 — — Pr H H H H — — — — H 631 Ir 2 1 Ph Iq2 — —Pr H H H H — — — — H 632 Ir 2 1 Ph Iq2 — — Iq2 H H H H — — — — H 633 Rh3 0 Ph Iq2 — — — F H F H — — — — H 634 Rh 3 0 Ph Iq2 — — — F H F H — — —— H 635 Rh 3 0 Ph Iq2 — — — F H F H — — — — H 636 Rh 2 1 Ph Iq2 Ph Pr —F H F H H H H H H 637 Pt 2 0 Ph Iq2 — — — F H F H — — — — H 638 Pt 2 0Ph Iq2 — — — F H F H — — — — H 639 Pd 2 0 Ph Iq2 — — — F H F H — — — — H640 Ir 3 0 Ph Iq6 — — — H H H H — — — — H 641 Ir 3 0 Ph Iq6 — — — H H FH — — — — H 642 Ir 3 0 Ph Iq6 — — — F H F H — — — — H 643 Ir 3 0 Ph Iq6— — — H CF3 H H — — — — H 644 Ir 3 0 Ph Iq6 — — — H CH3 H H — — — — H645 Ir 3 0 Ph Iq6 — — — H C4H9 H H — — — — H 646 Ir 3 0 Ph Iq6 — — — HC3F7 H H — — — — H 647 Ir 3 0 Ph Iq6 — — — H OC6H13 C3H7 H — — — — H 648Ir 3 0 Ph Iq6 — — — F F F H — — — — H 649 Ir 3 0 Ph Iq6 — — — H OCF3 H H— — — — H 650 Ir 3 0 Ph Iq7 — — — H H H H — — — — H 651 Ir 3 0 Ph Iq7 —— — H H F H — — — — H 652 Ir 3 0 Ph Iq7 — — — F H F H — — — — H 653 Ir 30 Ph Iq7 — — — H CF3 H H — — — — H 654 Ir 3 0 Ph Iq7 — — — H CH3 H H — —— — H 655 Ir 3 0 Ph Iq7 — — — H C4H9 H H — — — — H 656 Ir 3 0 Ph Iq7 — —— H C3F7 H H — — — — H 657 Ir 3 0 Ph Iq7 — — — H OC6H13 C3H7 H — — — — H658 Ir 3 0 Ph Iq7 — — — F F F H — — — — H 659 Ir 3 0 Ph Iq7 — — — H OCF3H H — — — — H B B′ B″ No R6 R7 R8 R9 R10 R5 R6 R7 R8 R9 R10 R5 R6 R7 R8R9 R10 620 H H H H H H H — H — — — — — — — — 621 H H H H H — H H H — — —— — — — — 622 H H H H H H — H H — — — — — — — — 623 H H H H H H H H H HH — — — — — — 624 H H H H H H — H H H H — — — — — — 625 H H H H H H H HH — — — — — — — — 626 H H H H H H H H H — — — — — — — — 627 H H H H H HH — — — — — — — — — — 628 H H H H H H H — — — — — — — — — — 629 H H H HH H H H H — — — — — — — — 630 H H H H H — — — — — — H H H H — — 631 H HH H H — — — — — — H H CH3 H — — 632 H H H H H — — — — — — H H H H H H633 H H F H H — — — — — — — — — — — — 634 H H F H H — — — — — — — — — —— — 635 H H F H H — — — — — — — — — — — — 636 H H F H H H H H H — — — —— — — — 637 H H H F H — — — — — — — — — — — — 638 H H H F H — — — — — —— — — — — — 639 H H H F H — — — — — — — — — — — — 640 H H — H H — — — —— — — — — — — — 641 H H — H H — — — — — — — — — — — — 642 H H — F H — —— — — — — — — — — — 643 H H — CF3 H — — — — — — — — — — — — 644 H H — HH — — — — — — — — — — — — 645 H H — H H — — — — — — — — — — — — 646 H H— H H — — — — — — — — — — — — 647 H H — H H — — — — — — — — — — — — 648H H — CF3 H — — — — — — — — — — — — 649 H H — H H — — — — — — — — — — —— 650 H H H — H — — — — — — — — — — — — 651 H H H — H — — — — — — — — —— — — 652 H H H — H — — — — — — — — — — — — 653 H H CF3 — H — — — — — —— — — — — — 654 H H H — H — — — — — — — — — — — — 655 H H H — H — — — —— — — — — — — — 656 H H H — H — — — — — — — — — — — — 657 H H H — H — —— — — — — — — — — — 658 H H F — H — — — — — — — — — — — — 659 H H H — H— — — — — — — — — — — —

TABLE 19 A B No M m′ A B R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 660 Ir 2 Ph Iq2H H H H H H H H H H 661 Ir 2 Ph Iq2 H CH3 H H H H H H H H 662 Ir 2 PhIq2 H C2H5 H H H H H H H H 663 Ir 2 Ph Iq2 H C3H7 H H H H H H H H 664 Ir2 Ph Iq2 H C4H9 H H H H H H H H 665 Ir 2 Ph Iq2 H C(CH3)3 H H H H H H HH 666 Ir 2 Ph Iq2 H C5H11 H H H H H H H H 667 Ir 2 Ph Iq2 H C6H13 H H HH H H H H 668 Ir 2 Ph Iq2 H C7H15 H H H H H H H H 669 Ir 2 Ph Iq2 HC8H17 H H H H H H H H 670 Ir 2 Ph Iq2 H C9H19 H H H H H H H H 671 Ir 2Ph Iq2 H C10H21 H H H H H H H H 672 Ir 2 Ph Iq2 H C11H23 H H H H H H H H673 Ir 2 Ph Iq2 H C12H25 H H H H H H H H 674 Ir 2 Ph Iq2 H C13H27 H H HH H H H H 675 Ir 2 Ph Iq2 H C14H29 H H H H H H H H 676 Ir 2 Ph Iq2 HC15H31 H H H H H H H H 677 Ir 2 Ph Iq2 H C16H33 H H H H H H H H 678 Ir 2Ph Iq2 H C17H35 H H H H H H H H 679 Ir 2 Ph Iq2 H C18H37 H H H H H H H H680 Ir 2 Ph Iq2 H C19H39 H H H H H H H H 681 Ir 2 Ph Iq2 H C20H41 H H HH H H H H 682 Ir 2 Ph Iq2 F H H H H H H H H H 683 Ir 2 Ph Iq2 H F H H HH H H H H 684 Ir 2 Ph Iq2 H H F H H H H H H H 685 Ir 2 Ph Iq2 H H H F HH H H H H 686 Ir 2 Ph Iq2 F H F H H H H H H H 687 Ir 2 Ph Iq2 H F F H HH H H H H 688 Ir 2 Ph Iq2 H F H F H H H H H H 689 Ir 2 Ph Iq2 F F F H HH H H H H

TABLE 20 A B No M m′ A B R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 690 Ir 2 Ph Iq2F F F F H H H CF3 H H 691 Ir 2 Ph Iq2 H CF3 H H H H H H CF3 H 692 Ir 2Ph Iq2 H H CF3 H H H H H CF3 H 693 Ir 2 Ph Iq2 H H H CF3 H H H H H H 694Ir 2 Ph Iq2 CF3 H CF3 H H H H H CF3 H 695 Ir 2 Ph Iq2 H CH3 F F H H H HH H 696 Ir 2 Ph Iq2 H C2H5 F F H H H H F H 697 Ir 2 Ph Iq2 H C3H7 F F HH H H H H 698 Ir 2 Ph Iq2 H C4H9 F F H H H H F H 699 Ir 2 Ph Iq2 H C5H11F F H H H H H H 700 Ir 2 Ph Iq2 H C6H13 F F H H H H CF3 H 701 Ir 2 PhIq2 H C12H25 F F H H H H H H 702 Ir 2 Ph Iq2 H C15H31 F F H H H H H H703 Ir 2 Ph Iq2 H C20H41 F F H H H H H H 704 Ir 2 Ph Iq2 H H H H H H H FH H 705 Ir 2 Ph Iq2 H H H H H H H H F H 706 Ir 2 Ph Iq2 H H H H H H HCF3 H H 707 Ir 2 Ph Iq2 H H H H H H H H CF3 H 708 Ir 2 Ph Iq2 H H H H FF F F F F 709 Ir 2 Ph Iq2 F F F F F F F F F F 710 Ir 2 Ph Iq2 H CF3 H HH H H F H H 711 Ir 2 Ph Iq2 H C2F5 H H H H H H H H 712 Ir 2 Ph Iq2 HC3F7 H H H H H H H H 713 Ir 2 Ph Iq2 H C4F9 H H H H H H CF3 H 714 Ir 2Ph Iq2 H C5F11 H H H H H H H H 715 Ir 2 Ph Iq2 H C6F13 H H H H H H H H716 Ir 2 Ph Iq2 H C7F15 H H H H H H CF3 H 717 Ir 2 Ph Iq2 H C8F17 H H HH H H H H 718 Ir 2 Ph Iq2 H C10F21 H H H H H H H H 719 Ir 2 Ph Iq2 HC15F31 H H H H H H H H

TABLE 21 A B No M m′ A B R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 720 Ir 2 Ph Iq2H

H H H H H H H H 721 Ir 2 Ph Iq2 H H CH3 H H H H H H H 722 Ir 2 Ph Iq2 HH

H H H H H H H 723 Ir 2 Ph Iq2 H H C2H5 H H H H H H H 724 Ir 2 Ph Iq2 H HC3H7 H H H H H H H 725 Ir 2 Ph Iq2 H H C4H9 H H H H H H H 726 Ir 2 PhIq2 H H C(CH3)3 H H H H H H H 727 Ir 2 Ph Iq2 H H C5H11 H H H H H H H728 Ir 2 Ph Iq2 H H C6H13 H H H H H H H 729 Ir 2 Ph Iq2 H H C7H15 H H HH H H H 730 Ir 2 Ph Iq2 H H C8H17 H H H H H H H 731 Ir 2 Ph Iq2 H HC9H19 H H H H H H H 732 Ir 2 Ph Iq2 H H C10H21 H H H H H H H 733 Ir 2 PhIq2 H H C11H23 H H H H H H H 734 Ir 2 Ph Iq2 H H C12H25 H H H H H H H735 Ir 2 Ph Iq2 H H C15H31 H H H H H H H 736 Ir 2 Ph Iq2 H H C18H37 H HH H H H H 737 Ir 2 Ph Iq2 H H C20H41 H H H H H H H 738 Ir 2 Ph Iq2 H FCH3 H H H H H H H 739 Ir 2 Fl Iq2 H H — — H H H H H H 740 Ir 2 Tn1 Iq2 HH — — H H H H H H 741 Ir 2 Tn2 Iq2 H H — — H H H H H H 742 Ir 2 Tn3 Iq2H H — — H H H H H H 743 Ir 2 Tn4 Iq2 H H — — H H H H H H 744 Ir 2 Np1Iq2 H H — — H H H H H H 745 Ir 2 Np2 Iq2 H H — — H H H H H H 746 Ir 2Cn1 Iq2 H H — — H H H H H H 747 Ir 2 Cn2 Iq2 H H — — H H H H H H 748 Ir2 Pe Iq2 H H — — H H H H H H 749 Ir 2 Qn1 Iq2 H H — — H H H H H H 750 Ir2 Qn2 Iq2 H H — — H H H H H H

TABLE 22 A B No M m′ A B R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 751 Ir 2 Cz Iq2H C2H5 — — H H H H H H 752 Ir 2 Ph Iq5 H H CF3 H — H H H H H 753 Ir 2 PhIq5 H H H CF3 — H H H H H 754 Ir 2 Ph Iq5 CF3 H CF3 H — H H H H H 755 Ir2 Ph Iq5 H H H H — H H H H H 756 Ir 2 Ph Iq5 H CH3 F F — H H H H H 757Ir 2 Ph Iq5 H C2H5 F F — H H H H H 758 Ir 2 Ph Iq5 H C3H7 F F — H H H HH 759 Ir 2 Ph Iq5 H C4H9 F F — H H H H H 760 Ir 2 Ph Iq5 H C5H11 F F — HH H H H 761 Ir 2 Ph Iq5 H C6H13 F F — H H H H H 762 Ir 2 Ph Iq5 H C6F13H H — H H H H H 763 Ir 2 Ph Iq6 H H H H H H H — H H 764 Ir 2 Ph Iq6 H HF H H H H — H H 765 Ir 2 Ph Iq6 F H F H H H H — F H 766 Ir 2 Ph Iq6 HCF3 H H H H H — CF3 H 767 Ir 2 Ph Iq6 H CH3 H H H H H — H H 768 Ir 2 PhIq6 H C4H9 H H H H H — H H 769 Ir 2 Ph Iq6 H C3F7 H H H H H — H H 770 Ir2 Ph Iq6 H OC6H13 C3H7 H H H H — H H 771 Ir 2 Ph Iq6 F F F H H H H — CF3H 772 Ir 2 Ph Iq6 H OCF3 H H H H H — H H 773 Ir 2 Ph Iq7 H H H H H H H H— H 774 Ir 2 Ph Iq7 H H F H H H H H — H 775 Ir 2 Ph Iq7 F H F H H H H H— H 776 Ir 2 Ph Iq7 H CF3 H H H H H CF3 — H 777 Ir 2 Ph Iq7 H CH3 H H HH H H — H 778 Ir 2 Ph Iq7 H C4H9 H H H H H H — H 779 Ir 2 Ph Iq7 H C3F7H H H H H H — H 780 Ir 2 Ph Iq7 H OC6H13 C3H7 H H H H H — H 781 Ir 2 PhIq7 F F F H H H H F — H 782 Ir 2 Ph Iq7 H OCF3 H H H H H H — H

TABLE 23 A B No M m n A B R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 783 Ir 3 0 PhIq8 H H H H H — H H H H 784 Ir 3 0 Ph Iq8 H H F H H — H H H H 785 Ir 3 0Ph Iq8 F H F H H — H H F H 786 Ir 3 0 Ph Iq8 H CF3 H H H — H H CF3 H 787Ir 3 0 Ph Iq8 H CH3 H H H — H H H H 788 Ir 3 0 Ph Iq8 H C4H9 H H H — H HH H 789 Ir 3 0 Ph Iq8 H C3F7 H H H — H H H H 790 Ir 3 0 Ph Iq8 H OC6H13C3H7 H H — H H H H 791 Ir 3 0 Ph Iq8 F F F H H — H H CF3 H 792 Ir 3 0 PhIq8 H OCF3 H H H — H H H H 793 Ir 3 0 Ph Iq9 H H H H H H — H H H 794 Ir3 0 Ph Iq9 H H F H H H — H H H 795 Ir 3 0 Ph Iq9 F H F H H H — H F H 796Ir 3 0 Ph Iq9 H CF3 H H H H — H CF3 H 797 Ir 3 0 Ph Iq9 H CH3 H H H H —H H H 798 Ir 3 0 Ph Iq9 H C4H9 H H H H — H H H 799 Ir 3 0 Ph Iq9 H C3F7H H H H — H H H 800 Ir 3 0 Ph Iq9 H OC6H13 C3H7 H H H — H H H 801 Ir 3 0Ph Iq9 F F F H H H — H CF3 H 802 Ir 3 0 Ph Iq9 H OCF3 H H H H — H H H803 Ir 3 0 Ph Iq10 H H H H H H H H H — 804 Ir 3 0 Ph Iq10 H H F H H H HH H — 805 Ir 3 0 Ph Iq10 F H F H H H H H F — 806 Ir 3 0 Ph Iq10 H CF3 HH H H H H CF3 — 807 Ir 3 0 Ph Iq10 H CH3 H H H H H H H — 808 Ir 3 0 PhIq10 H C4H9 H H H H H H H — 809 Ir 3 0 Ph Iq10 H C3F7 H H H H H H H —810 Ir 3 0 Ph Iq10 H OC6H13 C3H7 H H H H H H — 811 Ir 3 0 Ph Iq10 F F FH H H H H CF3 — 812 Ir 3 0 Ph Iq10 H OCF3 H H H H H H H —

EXAMPLES

Hereinbelow, the present invention will be described more specificallybased on Examples.

Examples 1 and 2

In these Examples, a device (effective display area=3 mm²) having adevice structure including 4 organic layers as shown in FIG. 1(c) wasprepared. An alkali-free glass sheet was used as a transparent substrate15 and a 100 nm-thick indium oxide (ITO) film was formed by sputteringand patterned as a transparent electrode 14. Further, α-NPD representedby the above-mentioned structural formula was vacuum-deposited in alayer thickness of 40 nm thereon as a hole-transporting layer 13. Then,as an organic luminescence layer 12, the above-mentioned CBP as a hostmaterial and a prescribed metal coordination compound in an amount ofproviding 8 wt. % were co-vacuum deposited in a layer thickness of 30nm. Further, as an exciton diffusion-prevention layer 17. BCP wasvacuum-deposited in a thickness of 10 nm. Then, as anelectron-transporting layer 16, the above-mentioned Alq3 was subjectedto resistance heating vacuum deposition at a vacuum of 10⁻⁴ Pa to forman organic film in a thickness of 30 nm.

On the above, as a lower layer of a metal electrode layer 11, an AlLialloy film was disposed in a thickness of 15 nm, and a 100 nm-thick Alfilm was vacuum-deposited thereon to form a patterned metal electrode 11disposed opposite to the transparent electrode 14 and having anelectrode area of 3 mm².

As the ligands, Example Compound No. 1 (Example 1) and Example CompoundNo. 28 (Example 2) shown in Table 1 were used respectively.

The performances of the thus-obtained EL devices were measured by usinga micro-current meter (“4140B”, made by Hewlett-Packard Corp.) for acurrent-voltage characteristic and “BM7” (made by Topcon K.K.) for anemission luminance. The devices using the respective coordinationcompounds respectively exhibited a good rectifying characteristic.

At an applied voltage of 12 volts, the EL devices exhibited luminancesas follows:

Device of Example 1 (Compound No. 1): 8000 cd/m²

Device of Example 2 (Compound No. 28): 3500 cd/m²

For examining luminescence characteristics of the Coordinate CompoundsNo. 1 and No. 28, the solutions were subjected to measurement of aluminescence spectrum. More specifically, each solution having acoordination compound concentration of 10⁻⁴ mol/l in toluene (orchloroform) was illuminated with excitation light of around 350 nm tomeasure a luminescence spectrum by using a spectral fluorophotometer(“F4500”, made by Hitachi K.K.). The luminescence spectra almostcoincided with the spectra from the EL devices at the time of voltageapplication, whereby it was confirmed that the luminescences of the ELdevices were emitted from the coordination compounds. (Refer to Example7 and 8 described hereinafter.)

Examples 3-5, Comparative Example 1

Luminescence devices were prepared in the same manner as in Examples 1and 2 except for using luminescence materials (Example Compounds) shownin Table 24 below. In Comparative Example 1, the above-mentionedIr(ppy)₃ was used as a representative of conventional luminescencematerial.

A current conduction durability test was performed for each device byapplying a DC voltage of 12 volts between the ITO electrode as the anodeand the Al electrode as the cathode to measure a time within which theluminance was attenuated to a half.

The measurement results are shown in Table 24 and the Example materialsexhibited a luminance half-attenuation period which was clearly longerthan the conventional luminescence material, thus providing a devicehaving a high durability attributable to the material of the presentinvention. TABLE 24 Luminescence Luminance half- material attenuationperiod Example No. (hours) 3 1 1550 4 24 1100 5 28 1350 Comp. 1 Ir(ppy)₃350

Example 6

A simple matrix type organic EL device as shown in FIG. 2 was preparedin the following manner.

On a glass substrate 21 measuring 100 mm-length, 100 mm-width and 1.1mm-thickness, a ca. 100 nm-thick ITO film was formed by sputtering andpatterned into 100 lines of 100 μm-wide transparent electrodes 22 (anodeside) with a spacing of 40 μm as simple matrix electrodes. Then, formedlayers of identical organic materials were found under identicalconditions as in Example 1 to form an organic compound layer 23.

Then, 100 lines of 100 μm-wide Al electrodes 24 were formed with aspacing of 40 μm by mask vacuum deposition so as to be perpendicular tothe transparent electrodes 22 by vacuum deposition at a vacuum of2.7×10⁻³ Pa. The metal electrodes (cathode) 24 were formed as alamination of 10 nm-thick layer of Al/Li alloy (Li: 1.3 wt. %) and then150 nm-thick layer of Al.

The thus-obtained 100×100-simple matrix-type organic EL device wassubjected to a simple matrix drive in a glove box filled with nitrogenat voltages of 7 volts to 13 volts by using a scanning signal of 10volts and data signals of ±3 volts. As a result of an interlaced driveat a frame efficiency of 30 Hz, respectively, luminescence images couldbe confirmed.

Example 7 Synthesis of Example Compound No. 1

69.3 g (448 mmol) of isoquinoline N-oxide (made by Tokyo Kasei) and 225ml of chloroform were placed and dissolved in a 1 liter-three-neckedflask, and under stirring and cooling with ice, 219.6 g (1432 mmol) ofphosphorus oxychloride was gradually added dropwise thereto while theinternal temperature was held at 15-20° C. Thereafter, the temperaturewas raised, and reflux under stirring was performed for 3 hours. Thereaction product was cooled by standing to room temperature and pouredinto iced water. After extraction with ethyl acetate, the organic layerwashed with water until neutrality, and the solvent was removed under areduced pressure to provide a dry solid, which was then purified bysilica gel column chromatography (eluent: chloroform/hexane=5/1) toobtain 35 5 g (yield: 44.9%) of 1-chloroisoquinoline white crystal.

In a 100 ml-three-necked flask, 3.04 g (24.9 mmole) of phenylboronicacid (made by Tokyo Kasei), 4.0 g of (25.0 mmole) of1-chloroisoquinoline, 25 ml of toluene, 12.5 ml of ethanol and 25 ml of2M-sodium carbonate aqueous solution were placed and stirred at roomtemperature under nitrogen stream, and 0.98 g (0.85 mmole) oftetrakis(triphenylphosphine)palladium (0) was added thereto. Thereafter,reflux under stirring was performed for 8 hours under nitrogen stream.After completion of the reaction, the reaction product was cooled andextracted by addition of cold water and toluene. The organic layer waswashed with saline water and dried on magnesium sulfate, followed byremoval of the solvent under a reduced pressure to provide dry solid.The residue was purified by silica gel column chromatography (eluent:chloroform/methanol 10/1) to obtain 2.20 g (yield=43.0%) of1-phenylisoquinoline. FIG. 7 shows a ¹H-NMR spectrum of a solution ofthe compound in heavy chloroform.

In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heatedat 130-140° C. under stirring and bubbling with nitrogen for 2 hours.Then, the glycerol was cooled by standing down to 100° C., and 1.03 g(5.02 mmole) of 1-phenylisoquinoline and 0.50 g (1.02 mmole) of iridium(III) acetyl-acetonate (made by Strem Chemicals, Inc.) were added,followed by 7 hours of heating-around ±210° C. under stirring andnitrogen stream. The reaction product was cooled to room temperature andinjected into 300 ml of 1N-hydrochloric acid to form a precipitate,which was filtered out and washed with water. The precipitate waspurified by silica gel column chromatography with chloroform as theeluent to obtain 0 22 g (yield=26.8%) of red powderytris(1-phenylisoquinoline-C²,N)iridium (III). According to MALDI-TOF MS(matrix-assisted laser desorption ionization-time of fight massspectroscopy), the compound exhibited M⁺ (mass number of thecorresponding cation formed by removal of 1 electron) of 805.2.

A solution in heavy chloroform of the compound provided a ¹H-NMRspectrum as shown in FIG. 8. A chloroform solution of the compoundexhibited a luminescence spectrum showing λmax=619 nm and a quantumyield of 0.66 relative to 1.0 of Ir(ppy)₃.

An EL device of Example 1 prepared by using the compound exhibited redluminescence showing λmax=620 nm under voltage application.

Example 8 Synthesis of Example Compound No. 28

In a 100 ml-three-necked flask, 2.91 g (12.2 mmole) of9,9-dimethylfluorene-2-boronic acid, 2.00 g (12.2 mmole) of1-chloroisoquinoline, 10 ml of toluene, 5 ml of ethanol and 10 ml of2M-sodium carbonate aqueous solution were placed and stirred at roomtemperature under nitrogen stream, and 0.44 g (0.38 mmole) oftetrakis(triphenylphosphine)palladium (0) was added thereto. Thereafter,reflux under stirring was performed for 5 hours under nitrogen stream.After completion of the reaction, the reaction product was cooled andextracted by addition of cold water and toluene. The organic layer waswashed with saline water and dried on magnesium sulfate, followed byremoval of the solvent under a reduced pressure to provide dry solid.The residue was purified by silica gel column chromatography (eluent:toluene/ethyl acetate=50/1) to obtain 2.13 g (yield=54.2%) of1-(9,9-dimethylfluorene-2-yl)isoquinoline.

In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heatedat 130-140° C. under stirring and bubbling with nitrogen for 2 hours.Then, the glycerol was cooled by standing down to 100° C., and 1.61 g(5.01 mmole) of 1-(9,9-dimethylfluorene-2-yl)isoquinoline and 0.50 g(1.02 mole) of iridium (III) acetylacetonate were added, followed by 8hours of reflux under stirring and nitrogen stream. The reaction productwas cooled to room temperature and injected into 600 ml of1N-hydrochloric acid to form a precipitate, which was filtered out andwashed with water. The precipitate was purified by silica gel columnchromatography with chloroform as the eluent to obtain 0.38 g(yield=32.3%) of red powderytris[1-(9,9-dimethylfluorene-2-yl)isoquinoline-C³,N]iridium (III).According to MALDI-TOF MS, the compound exhibited M′ of 1153.4.

A toluene solution of the compound exhibited a luminescence spectrumshowing λmax=648 nm and a quantum yield of 0.66 relative to 1.0 ofIr(ppy)₃.

An EL device of Example 2 prepared by using the compound exhibited redluminescence showing λmax=650 nm under voltage application.

Example 9 Synthesis of Example Compound No 25

In a 100 ml-three-necked flask, 4.45 g (25.0 mmole) ofthianaphthene-2-boronic acid (made by Aldrich Chemical Co., Inc.), 4.09g (25.0 mmole) of 1-chloroisoquinoline, 25 ml of toluene, 12.5 ml ofethanol and 25 mol of 2M-sodium carbonate aqueous solution were placedand stirred at room temperature under nitrogen stream, and 0.98 g (0.85mmole) of tetrakis(triphenylphosphine)palladium (0) was added thereto.Thereafter, reflux under stirring was performed for 8 hours undernitrogen stream. After completion of the reaction, the reaction productwas cooled and extracted by addition of cold water and toluene. Theorganic layer washed with saline water and dried on magnesium sulfate,followed by removal of the solvent under a reduced pressure to providedry solid. The residue was purified by silica gel column chromatography(eluent: chloroform) to obtain 4.20 g (yield=64-3%) of1-(thianaphthene-2-yl)isoquinoline.

In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heatedat 130-140° C. under stirring and bubbling with nitrogen for 2 hours.Then, the glycerol was cooled by standing to 100° C., and 1.31 g (5.01mmole) of 1-(thianaphthene-2-yl)-isoquinoline, and 0.50 g (1.02 mmole)of iridium (III) acetylacetone, were added, followed by 5 hours ofheating around 210° C. under stirring and nitrogen stream. The reactionproduct was cooled to room temperature and poured into 300 ml of1N-hydrochloric acid to form a precipitate, which was then filtered outand washed with water. The precipitate was purified by silica gel columnchromatography with chloroform as the eluent to obtain 0.25 g (yield25.2%) of red powderytris[1-(thianaphthene-2-yl)-isoquinoline-C³,N]iridium (III). Accordingto MALDI-TOF MS, M⁺ of the compound of 973.1 was confirmed. A toluenesolution of the compound exhibited a luminescence spectrum showingλmax=686 nm and a quantum yield of 0.07 relative to 1.0 of Ir(ppy)₃.

An EL device was prepared in the same manner as in Example 1 except forusing the compound instead of Compound No. 1 and was confirmed to emitdeep red luminescence under voltage application.

Example 10 Synthesis of Example Compound No. 24

In a 100 ml-three-necked flask, 2.56 g (20.0 mmole) of2-thiophene-2-boronic acid (made by Aldrich Co.), 3.27 g (20.0 mmole) of1-chloroisoquinoline, 18 ml of toluene, 9 ml of ethanol and 18 mol of2M-sodium carbonate aqueous solution were placed and stirred at roomtemperature under nitrogen stream, and 0.72 g (0.62 mmole) oftetrakis(triphenylphosphine)palladium (0) was added thereto. Thereafter,reflux under stirring was performed for 9 hours under nitrogen stream.After completion of the reaction, the reaction product was cooled andextracted by addition of cold water and toluene. The organic layer waswashed with saline water and dried on magnesium sulfate, followed byremoval of the solvent under a reduced pressure to provide dry solid.The residue was purified by silica gel column chromatography (eluent:chloroform) to obtain 2.40 g (yield 56.8%) of 1-(2-thienyl)isoquinoline.

In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heatedat 130-140° C. under stirring and bubbling with nitrogen for 2 hours.Then, the glycerol was cooled by standing to 100° C., and 1.05 g (4.97mmole) of 1-(2-thienyl)isoquinoline, and 0.50 g (1.02 mmole) of iridium(III) acetylacetone, were added, followed by 8 hours of reflux understirring and nitrogen stream. The reaction product was cooled to roomtemperature and poured into 600 ml of 1N-hydrochloric acid to form aprecipitate, which was then filtered out and washed with water. Theprecipitate was purified by silica gel column chromatography withchloroform as the eluent to obtain 0.38 g (yield=45.2%) of red powderytris[1-(2-thienyl)isoquinoline-C³,N]iridium (III). According toMALDI-TOF MS, M⁺ of the compound of 823.1 was confirmed. A toluenesolution of the compound exhibited a luminescence spectrum showingλmax=642 nm and a quantum yield of 0.43 relative to 1.0 of Ir(ppy)₃.

An EL device was prepared in the same manner as in Example 1 except forusing the compound instead of Compound No. 1 and was confirmed to emitred luminescence showing λmax=640 nm under voltage application.

Example 11

In a 200 ml-three-necked flask, 3.40 g (25.0 mmole) of4-methylphenyl-boronic acid (made by Aldrich Co.), 4.09 g (25.0 mmole)of 1-chloroisoquinoline, 25 ml of toluene, 12.5 ml of ethanol and 25 molof 2M-sodium carbonate aqueous solution were placed and stirred at roomtemperature under nitrogen stream, and 0.98 g (0.85 mmole) oftetrakis(triphenylphosphine)-palladium (0) was added thereto.Thereafter, reflux under stirring was performed for 8 hours undernitrogen stream. After completion of the reaction, the reaction productwas cooled and extracted by addition of cold water and toluene. Theorganic layer washed with saline water and dried on magnesium sulfate,followed by removal of the solvent under a reduced pressure to providedry solid The residue was purified by silica gel column chromatography(eluent: chloroform/methanol=10/1) to obtain 2.80 g (yield=51.1%) of1-(4-methylphenyl)isoquinoline.

In a 200 ml-three-necked flask, 0.58 mg (1.64 mmole) of iridium (III)chloride-trihydrate (made by Acros Organics Co.), 1.61 g (7.34 mmole) of1-(4-methylphenyl)isoquinoline, 45 ml of ethanol and 15 ml of water wereplaced and stirred for 30 min. at room temperature under nitrogenstream, followed by 24 hours of reflux under stirring. The reactionproduct was cooled to room temperature, and the precipitate wasrecovered by filtration and washed with water, followed successivewashing with ethanol and acetone. After drying under a reduced pressureat room temperature, 1.02 g (yield=93.4%) of red powderytetrakis[1-(4-methylphenyl)isoquinoline-C²,N]-(μ-dichloro)diiridium(III) (Example Compound No. 661) was obtained. FIG. 10 shows a ¹H-NMRspectrum of a heavy chloroform solution of the compound. A toluenesolution of the compound exhibited a luminescence spectrum showingλmax=617 n and a quantum yield of 0.46 relative to 1.0 of Ir(ppy)₃.

In a 200 ml-three-necked flask, 70 ml of ethoxyethanol, 0.95 g (0.72mmole) oftetrakis[1-(4-methylphenyl)isoquinoline-C²,N](μ-dichloro)-diiridium(III). 0.22 g (2.10 mmole) of acetylacetone and 1.04 g (9.91 mmole) ofsodium carbonate, were placed and stirred for 1 hour at room temperatureunder nitrogen stream and then refluxed under stirring for 15 hours. Thereaction product-was cooled with ice, and the precipitate was filteredout and washed with water. The precipitate was then purified by silicagel column chromatography (eluent: chloroform/methanol=30/1) to obtain0.43 g (yield=41.3%) of red powderybis[1-(4-methylphenyl)isoquinoline-C²,N](acetylacetonato)-iridium (III)(Example Compound No. 43). According to MALDI-TOF MS, M⁺ of 728.2 of thecompound was confirmed. FIG. 11 shows a ¹H-NMR of a heavy chloroformsolution of the compound. A toluene solution of the compound exhibited aluminescence spectrum showing λmax=622 nm and a quantum yield of 0.70relative to 1.0 of Ir(ppy)₃.

In a 100 ml-three-necked flask, 0.27 g (1.27 mmole) of1-(4-methylphenyl)isoquinoline, 0.36 g (0.49 mmole) ofbis[1-(4-methylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)and 25 ml of glycerol, were placed and heated around 180° C. understirring and nitrogen stream. The reaction product was cooled to roomtemperature and poured into 170 ml of 1N-hydrochloric acid, and theprecipitate was filtered out, washed with water and dried at 100° C.under a reduced pressure for 5 hours. The precipitate was purified bysilica gel column chromatography with chloroform as the eluent to obtain0.27 g (yield=64.5%) of red powderytris[1-(4-methylphenyl)-isoquinoline-C²,N]iridium (III) (ExampleCompound No-19). According to MALDI-TOF MS, M⁺ of 847.3 of the compoundwas confirmed. FIG. 12 shows a ¹H-NMR spectrum of a heavy chloroformsolution of the compound. A toluene solution of the compound exhibited aluminescence spectrum showing λmax 619 nm and a quantum yield of 0.65relative to 1.0 of Ir(ppy)₃.

Example 12

The following compounds were successively produced in the same manner asin Example 11 except for using 4-n-hexylphenylboronic acid instead ofthe 4-methylphenylboronic acid.

Tetrakis[1-(4-n-hexylphenyl)isoquinoline-C²,N[(μ-dichloro)diiridium(Example Compound No. 667)

luminescence spectrum of toluene solution: λmax=616 nm

quantum yield=0.40 relative to 1.0 of Ir(ppy)₃.

Bis[1-(4-n-hexylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)(Example Compound No. 196)

MALDI-TOF MS:. M⁺868.4

luminescence spectrum of toluene solution: λmax=625 nm

quantum yield 0.87 relative to 1.0 of Ir(ppy)₃

Tris[1-(4-n-hexylphenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 192)

MALDI-TOF MS: M⁺=1057.5

luminescence spectrum of toluene solution: λmax=621 nm

quantum yield=0.88 relative to 1.0 of Ir(ppy)₃

Example 13

The following compounds were successively produced in the same manner asin Example 11 except for using 4-n-octylphenylboronic acid instead ofthe 4-methylphenylboronic acid.

Tetrakis[1-(4-n-octylphenyl)isoquinoline-C²,N[(μ-dichloro)diiridium(Example Compound No. 669)

luminescence spectrum of toluene solution: λmax=617 nm

quantum yield=0.47 relative to 1.0 of Ir(ppy)₃.

Bis[1-(4-n-octylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)(Example Compound No. 218)

MALDI-TOF MS: M⁺=924.4

luminescence spectrum of toluene solution: λmax=625 nm

quantum yield 1.05 relative to 1.0 of Ir(ppy)₃

FIG. 13 shows a ¹H-NMR spectrum of a heavy chloroform solution of thecompound.

Tris[1-4-n-octylphenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 214)

MALDI-TOF MS: M⁺=1141.6

luminescence spectrum of toluene solution: λmax=620 nm

quantum yield=0.75 relative to 1.0 of Ir(ppy)₃

Example 14

The following compounds were successively produced in the same manner asin Example 11 except for using 4-tert-butylphenylboronic acid (made byAldrich Co.) instead of the 4-methylphenylboronic acid.

Tetrakis[1-(4-t-butylphenyl)isoquinoline-C²,N](μ-dichloro)diiridium(Example Compound No. 665)

luminescence spectrum of toluene solution: λmax=614 nm

quantum yield=0.39 relative to 1.0 of Ir(ppy)₃.

Bis[1-(4-t-butylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)(Example Compound No. 174)

MALDI-TOF MS: M⁺=812.3

luminescence spectrum of toluene solution: λmax 626 nm quantum yield0.66 relative to 1.0 of Ir(ppy)₃

Tris[1-(4-t-butylphenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 170)

MALDI-TOF MS: M⁺=973.4

luminescence spectrum of toluene solution: λmax 618 nm

quantum yield=0.73 relative to 1.0 of Ir(ppy)₃

Example 15

The following compounds were successively produced in the same manner asin Example 11 except for using 3-fluorophenylboronic acid (made byAldrich Co.) instead of the 4-methylphenylboronic acid.

Tetrakis[1-(5-fluorophenyl)isoquinoline-C²,N](μ-dichloro)diiridium(Example Compound No 684)

luminescence spectrum of toluene solution: λmax=625 nm

quantum yield=0.22 relative to 1.0 of Ir(ppy)₃

Bis[1-(5-fluorophenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)(Example Compound No. 47)

MALDI-TOF MS: M⁺=736.2

luminescence spectrum of toluene solution: λmax=629 nm

quantum yield=0.65 relative to 1.0 of Ir(ppy)₃

Tris[1-(5-fluorophenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 23)

MALDI-TOF MS: M⁺=859.2

luminescence spectrum of toluene solution: λmax=626 nm

quantum yield=0.62 relative to 1.0 of Ir(ppy)₃

Example 16

The following compounds were successively produced in the same manner asin Example 11 except for using 4-phenoxyphenylboronic acid instead ofthe 4-methylphenylboronic acid.

Bis[1-(4-phenoxyphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)(Example Compound No. 365)

MALDI-TOF MS: M⁺=884.2

luminescence spectrum of toluene solution: λmax=608 nm

quantum yield=0.65 relative to 1.0 of Ir(ppy)₃

Tris[1-(4-phenoxyphenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 361)

MALDI-TOF MS: M⁺=1081.3

luminescence spectrum of toluene solution: λmax=604 nm

quantum yield=0.54 relative to 1.0 of Ir(ppy)₃

Example 17

The following compounds were successively produced in the same manner asin Example 11 except for using 3-methylphenylboronic acid instead of the4-methylphenylboronic acid.

BiS[1-(4-5-methylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) (Example Compound No. 44)

MALDI-TOF MS: M⁺=728.2

luminescence spectrum of toluene solution: λmax=638 nm

quantum yield=0.78 relative to 1.0 of Ir(ppy)₃

Tris[1-(4-5-methylphenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 20)

MALDI-TOF MS: M⁺=847.3

luminescence spectrum of toluene solution: λmax=631 nm

quantum yield=. 0.71 relative to 1.0 of Ir(ppy)₃

Example 18

1-phenylisoquinoline synthesized in Example 7 was used instead of the1-(4-methylphenyl)isoquinoline used in Example 11, and the followingcompound was prepared in a similar manner as in Example 11 viatetrakis(1-phenylisoquinoline-C², N)(μ-dichloro)-diiridium (III)(Example Compound No. 660).

Bis(1-phenylisoquinoline-C², N)(acetylacetonato)-iridium (III) (ExampleCompound No. 42)

MALDI-TOF MS: M⁺=700.2

luminescence spectrum of toluene solution: λmax 604 nm

quantum yield 0.54 relative to 1.0 of Ir(ppy)₃

Example 19

1-(biphenyl-3-yl)isoquinoline was synthesized by using 3-biphenylboronicacid (made by Frontier Scientific, Inc.) instead of phenylboronic acidin Example 7. and similarly as in Example 7,tris[1-(biphenyl-3-yl)isoquinoline-C²,N]iridium (III) (Example CompoundNo-3) was prepared from the 1-(biphenyl-3-yl)isoquinoline and iridium(III) acetylacetonate. According to MALDI-TOF MS, M⁺ of the compound of1033.3 was confirmed. A toluene solution of the compound exhibited aluminescence spectrum showing λmax=621 nm and a quantum yield of 0.53relative to 1.0 of Ir(ppy)₃.

Example 20

3-methyl-2,4-pentanedione (made by Aldrich Co.) instead of acetylacetonein Example 11, and similarly as in Example 11,bis[1-(4-methylphenyl)-isoquinoline-C²,N](3-methyl-2,4-pentanedionato)-iridium(III) (Example Compound No. 126) was synthesized. According to MALDI-TOFMS, M⁺ of the compound of 742.2 was confirmed. A toluene solution of thecompound exhibited a luminescence spectrum showing λmax 627 nm and aquantum yield of 0.81 relative to 1.0 of Ir(ppy)₃.

Example 21

2,2,6,6-tetramethyl-3,5-heptanedione (made by Tokyo Kasei Kogyo) wasused instead of acetylacetone in Example 11, and similarly as in Example11,bis[1-(4-methylphenyl)isoquinoline-C²,N](2,2,6,6-tetramethyl-3,5-heptanedionato)iridium(III) (Example Compound No. 127) was synthesized. According to MALDI-TOFMS, M⁺ of the compound of 812.3 was confirmed A toluene solution of thecompound exhibited a luminescence spectrum showing λmax 624 nm and aquantum yield of 0.76 relative to 1.0 of Ir(ppy)₃.

Example 22

2-Phenylpyridine was used instead of the 1-(4-methylphenyl)isoquinolineused in Example 11, and similarly as in Example 11,bis(2-phenylpyridine-C²,N)(acetylacetonato)iridium (III) was synthesizedvia (2-phenylpyridine-C²,N)(μ-dichloro)diiridium (III). The compound wasreacted with 1-phenylisoquinoline synthesized in Example 7 in a similarmanner as in Example 11 to obtainbis(2-phenylpyridine-C²,N)(1-phenylisoquinoline-C²,N)iridium (III)(Example Compound No. 64) According to MALDI-TOF MS, M⁺ of the compoundof 705.2 was confirmed. A toluene solution of the compound exhibited aluminescence spectrum showing % max=618 nm and a quantum yield of 0.43relative to 1.0 of Ir(ppy)₃.

Example 23

Bis(1-phenylisoquinoline-C²,N)(acetyl-acetonato)iridium (III)synthesized in Example 18 and 2-phenylpyridine were reacted in a similarmanner as in Example 22 to obtainbis(1-phenylisoquinoline-C²,N)(2-phenylpyridine-C²,N)iridium (III)(Example Compound No. 31). According to MALDI-TOF MS, M⁺ of the compoundof 755.2 was confirmed. A toluene solution of the compound exhibited aluminescence spectrum showing λmax=617 nm and a quantum yield of 0.46relative to 1.0 of Ir(ppy)₃.

Example 24

The following compounds were successively produced in the same manner asin Example 11 except for using 4-butylphenylboronic acid (made byLancaster Synthesis Co.) instead of the 4-methylphenylboronic acid.

Tetrakis[1-(4-n-butylphenyl)isoquinoline-C²,N](μ-dichloro)diiridium(Example Compound No. 664)

luminescence spectrum of toluene solution: λmax=629 nm

quantum yield 0.44 relative to 1.0 of Ir(ppy)₃.

Bis[1-(4-butylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)(Example Compound No. 163)

MALDI-TOF MS: M⁺=812.0

luminescence spectrum of toluene solution: λmax=626 nm

quantum yield=0.81 relative to 1.0 of Ir(ppy)₃

Tris[1-(4-butylphenyl)isoquinoline-C²,N]-iridium (III) (Example CompoundNo. 159)

MALDI-TOF MS: M⁺=973.3

luminescence spectrum of toluene solution: λmax=621 nm

quantum yield=0.82 relative to 1.0 of Ir(ppy)₃.

Example 25

5-Aminoisoquinoline (made by Tokyo Kasei Kogyo K.K.) was used tosynthesize 1-chloro-5-fluoroisoquinoline along the following path withyields as indicated.

In the process of Example 11, phenylboronic acid was used instead of the4-methylphenyl-boronic acid and 1-chloro-5-fluoroisoquinoline was usedinstead of the 1-chloroisoquinoline to synthesize1-phenyl-5-fluoroisoquinoline, which was used instead of the1-(4-methylphenyl)isoquinoline otherwise in a similar manner as inExample 11 to synthesize the following compounds successively.

Tetrakis(1-phenyl-5-fluoroisoquinoline-C²,N)(μ-dichloro)diiridium (III)(Example Compound No. 704)

luminescence spectrum of toluene solution: λmax=620 nm

quantum yield=0.38 relative to 1.0 of Ir(ppy)₃.

Bis(1-phenyl-5-fluoroisoquinoline-C²,N)-(acetylacetonato)iridium (III)(Example Compound No. 240)

MALDI-TOF MS: M⁺=735.8

luminescence spectrum of toluene solution: λmax=636 nm

quantum yield 0.70 relative to 1.0 of Ir(ppy)₃

Tris(1-phenyl-5-fluoroisoquinoline-C²,N]-iridium (III) (Example CompoundNo. 155)

MALDI-TOF MS: M⁺=858.9

luminescence spectrum of toluene solution: λmax=628 nm

quantum yield=0.55 relative to 1.0 of Ir(ppy)₃

Example 26

3-Nitro-2-hydroxypyridine (made by Aldrich Co.) was used to synthesize1-chloro-8-azaisoquinoline along the following path. “Sulfo mix” usedfor the ring closure was prepared through a process described in J. Org.Chem., 1943, 8, 544-549.

The above-obtained 1-chloro-8-azaisoquinoline was used instead of the1-chloroisoquinoline in Example 7 to synthesize1-phenyl-8-azaisoquinoline, which was used instead of the1-(4-methylphenyl)-isoquinoline otherwise in the same manner as inExample 11 to prepare the following compounds successively.

Tetrakis(1-phenyl-8-azaphenylisoquinoline-C²,N)(μ-dichloro)diiridium(III) (Example Compound No. 755)

luminescence spectrum of toluene solution: λmax=635 nm

quantum yield=0.40 relative to 1.0 of Ir(ppy)₃.

Bis(1-phenyl-8-azaphenylisoquinoline-C²,N)-(acetylacetonato)iridium(III) (Example Compound No. 612)

MALDI-TOF MS: M⁺=701.1

luminescence spectrum of toluene solution: λmax 631 nm

Tris(1-phenyl-8-azaphenylisoquinoline-C²,N)-iridium (III) (ExampleCompound No. 609)

MALDI-TOF MS: M⁺=807.9

luminescence spectrum of toluene solution: λmax=622 nm

Example 27

An EL device having a laminate structure as shown in FIG. 1(b) wasprepared. On an ITO electrode 14 patterned on a 1.1 mm-thick alkali-freeglass substrate 15, α-NPD was deposited in a thickness of 40 nm at avacuum deposition rate of 0.1 nm/sec at a vacuum pressure of 10⁻⁴ Pa toform a hole-transporting layer 13, and then CBP andtris(1-phenylisoquinoline-C²,N)iridium (III) (Example. Compound No. 1)in an amount of providing a concentration of 9% were co-vacuum-depositedto form a 40 nm-thick luminescence layer 12 while controlling theheating conditions of the vacuum deposition boats so as to providevacuum deposition rates of 0.1 nm/sec for CBP and 0.09 nm/sec for theiridium complex.

Then, an electron-transporting layer was formed in a thickness of 40 nmby vacuum deposition of bathophenanthroline Bphen represented by astructural formula shown below at a rate of 0.1 nm/sec.

Thereon a ca. 1 nm-thick potassium fluoride layer was formed as anelectron-transporting layer 16 by vacuum deposition at a rate of 0.5nm/sec, and then aluminum was vacuum-deposited in a thickness of 150 nmat a rate of 1 nm/sec to provide a cathode metal 11.

The device of this Example was prepared-while aiming at the effects of(1) increased supply of electrons and suppression of hole leakage by useof Bphen, (2) improved electron-injection characteristic by use of KFand (3) optmization of optical layer thickness. Thevoltage-efficiency-luminance characteristics of the thus-obtained deviceare shown in FIG. 5.

The device of this Example succeeded in realizing efficiencies of 6.2lm/W and 5.2 lm/W at luminances of 100 cd/m² and 300 cd/m²,respectively. CIE coordinates were (0.68, 0.317) at 40 cd/m² (0.682,0.315) at 113 cd/m² and (0.678, 0.317) at 980 cd/m², thus showing that asufficient color purity was provided according to a color standard ofthe NTSC. Thus, the luminescence color was substantially unchanged atdifferent luminances and voltages.

Tris(1-phenylisoquinoline-C²,N)iridium (III) having a ligand of1-phenylisoquinoline can provide red luminescence according to the NTSCstandard even without adding a substituent to the ligand skeleton forluminescence color adjustment of the complex, and is thus excellent as ared luminescence material. Further, it is also a desirable luminescencematerial from a practical viewpoint of shorter synthesis steps as theeffect is attained by using a ligand having no substituent.

The drive conditions included an application voltage V=5 volts and acurrent J=1.5 mA/cm² at a luminance of 300 cd/m², and also 10 volts and520 mA/cm² at 14000 cd/m². The external quantum efficiency (E.Q.E.)values (%) of the thus-prepared EL device are plotted on FIG. 6 andshowing efficiencies remarkably improving the efficiency of theconventional EL device, e.g., over 10. % at 100 cd/m².

Example 28

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-ethylphenylboronic acid(made by Lancaster Co.) instead of the 4-methylphenylboronic acid inExample 11.

Tetrakis[1-(4-ethylphenyl)isoquinoline-C², N(μ-dichloro)iridium (III)(Example Compound No. 662)Bis[1-(4-ethylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)(Example Compound No. 137)Tris[1-(4-ethylphenyl)isoquinoline-C²,N]-iridium (III) (Example CompoundNo. 135) Example 29

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-propylphenylboronic acidinstead of the 4-methylphenylboronic acid in Example 11.

Tetrakis[1-(4-propylphenyl)isoquinoline-C²,N](μ-dichloro)iridium (III)(Example Compound No. 663)Bis[1-(4-propylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)(Example Compound No. 148) Tris[1-(4-propylphenyl)isoquinoline-C²,N]-iridium (III) (Example Compound No. 144) Example 30

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-isopropylphenylboronicacid (made by Lancaster Co.) instead of the 4-methyl-phenylboronic acidin Example 11.

Tetrakis[1-(4-isopropylphenyl)isoquinoline-C²,N](μ-dichloro)iridium(III)Bis[1-(4-isopropylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) Tris[1-(4-isopropylphenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 146) Example 31

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-n-pentylphenylboronicacid instead of the 4-methylphenylboronic acid in Example 11.

Tetrakis[1-(4-n-pentylphenyl)isoquinoline-C²,N](μ-dichloro)iridium (III)(Example Compound No. 666)Bis[1-(4-n-pentylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) (Example Compound No. 185)Tris[1-(4-n-pentylphenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 181) Example 32

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-n-heptylphenylboronicacid instead of the 4-methylphenylboronic acid in Example 11.

Tetrakis[1-(4-n-heptylphenyl)isoquinoline-C²,N](μ-dichloro)iridium (III)(Example Compound No-668)Bis[1-(4-n-heptylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) (Example Compound No. 207)Tris[1-(4-n-heptylphenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No-203) Example 33

The following compounds were successively produced in the same manner asin Example 11 except for using 4-fluorophenylboronic acid (made byAldrich Co.) instead of the 4-methylphenylboronic acid.

Tetrakis[1-(4-n-hexylphenyl)isoquinoline-C²,N[(μ-dichloro)diiridium(Example Compound No 683)

luminescence spectrum of toluene solution: λmax 602 nm

quantum yield=0.40 relative to 1.0 of Ir(ppy)₃.

Bis[1-(4-fluorohexylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) (Example Compound No. 46)

MALDI-TOF MS: M⁺=737.2

luminescence spectrum of toluene solution: λmax=603 nm

quantum yield=0.95 relative to 1.0 of Ir(ppy)₃

Tris[1-(4-fluorophenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 22)

MALDI-TOF MS: M⁺=859.2

luminescence spectrum of toluene solution: λmax=596 nm

quantum yield 0.92 relative to 1.0 of Ir(ppy)₃

Example 34

The following compounds were successively produced in the same manner asin Example 11 except for using 4-fluoro-3-methylphenylboronic acid (madeby Aldrich Co.) instead of the 4-methylphenylboronic acid.

Tetrakis[1-(4-fluoro-5-methylphenyl)isoquinoline-C²,N](μ-dichloro)diiridium(Example Compound No. 738)

luminescence spectrum of toluene solution: λmax=618 nm

Bis[1-(4-fluoro-5-methylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III) (Example Compound No. 222)

MALDI-TOF MS: M⁺=765.2

luminescence spectrum of toluene solution: λmax=615 nm

Tris[1-(4-fluoro-5-methylphenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 226)

MALDI-TOF MS: M⁺=901.1

luminescence spectrum of toluene solution: λmax=616 nm

Example 35

The following compounds were successively produced in the same manner asin Example 11 except for using 4-trifluoromethylphenylboronic acid (madeby Lancaster Co.) instead of the 4-methylphenylboronic acid.

Tetrakis[1-(4-trifluoromethylphenyl)isoquinoline-C²,N(μ-dichloro)diiridium

luminescence spectrum of toluene solution: λmax=614 nm

Bis[1-(4-tritluoromethylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III)

MALDI-TOF MS: M⁺=836.1

luminescence spectrum of toluene solution: λmax=623 nm

quantum yield=0.23 relative to 1.0 of Ir(ppy)₃

Tris(1-(4-trifluoromethylphenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 11)

MALDI-TOF MS: M⁺=1009.2

luminescence spectrum of toluene solution: λmax 608 nm

quantum yield 0.48 relative to 1.0 of Ir(ppy)₃.

Example 36

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using3-trifluoromethylphenylboronic acid (made by Lancaster Co.) instead ofthe 4-methylphenylboronic acid in Example II.

Tetrakis[1-(5-trifluoromethylphenyl)isoquinoline-C²,N](μ-dichloro)iridium(III)Bis[1-(5-trifluoromethylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) Tris[1-(5-trifluoromethylphenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 12) Example 37

The following compounds were successively produced in the same manner asin Example 11 except for using 3,5-difluoro-3-methylphenylboronic acid(made by Aldrich Co.) instead of the 4-methyl-phenylboronic acid.

Tetrakis[1-(3,5-difluoro-3-methylphenyl)iso-quinoline-C²,N](μ-dichloro)diiridium(Example Compound No. 686)

luminescence spectrum of toluene solution: λmax=618 nm

Bis[1-(3,5-fluoro-3-methylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) (Example Compound No. 425)

MALDI-TOF MS: M⁺=765.2

luminescence spectrum of toluene solution: λmax=625 nm

Tris[1-(3,5-difluoro-3-methylphenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 421)

MALDI-TOF MS: M⁺=901.2

luminescence spectrum of toluene solution: λmax 616 nm

Example 38

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 2,3-difluorophenylboronicacid instead of the 4-methylphenylboronic acid in Example 11.

Tetrakis[1-(5,6-difluorophenyl)isoquinoline-C²,N](μ-dichloro)iridium(III)Bis[1-(5,6-difluorophenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) (Example Compound No. 501)Tris[1-(5,6-difluorophenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 497) Example 39

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using2,3-difluoro-4-n-butylphenyl-boronic acid instead of the4-methylphenylboronic acid in Example 11.

Tetrakis[1-(4-n-butyl-5,6-difluorophenyl)-isoquinoline-C²,N](μ-dichloro)iridium(III) (Example Compound No. 698)Bis[1-(4-n-butyl-5,6-difluorophenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) (Example Compound No. 534)Tris[1-(4-n-butyl-5,6-difluorophenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 530) Example 40

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using1-phenyl-5-trifluoromethyl-isoquinoline, synthesized in the same manneras in Example 7 by using 1-chloro-5-trifluoromethyl-isoquinoline insteadof the 1-chloroisoquinoline in Example 7.

Tetrakis[1-phenyl-5-trifluoromethylisoquinoline-C²,N](μ-dichloro)iridium(III) (Example Compound No. 706)Bis[1-phenyl-5-trifluoromethylisoquinoline-C²,N]-(acetylacetonato)iridium(III) Tris[1-phenyl-5-trifluoromethylisoquinoline-C²,N]-iridium (III)(Example Compound No. 83) Example 41

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using1-phenyl-4-trifluoromethyl-isoquinoline, synthesized in the same manneras in Example 7 by using 1-chloro-4-trifluoromethyl-isoquinoline insteadof the 1-chloroisoquinoline in Example 7.

Tetrakis[1-phenyl-4-trifluoromethylisoquinoline-C²,N](μ-dichloro)iridium(III) (Example Compound No. 706)Bis[1-phenyl-4-trifluoromethylisoquinoline-C²,N]-(acetylacetonato)iridium(III) Tris(1-phenyl-4-trifluoromethylisoquinoline-C²,N)-iridium (III)(Example Compound No 82) Example 42

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using1-phenyl-4-trifluoromethyl-isoquinoline, synthesized in the same manneras in Example 7 by using 1-chloro-4-trifluoromethyl-isoquinoline insteadof the 1-chloroisoquinoline in Example 7.

Tetrakis[1-phenyl-4-trifluoroisoquinoline-C²,N](μ-dichloro)iridium (III)(Example Compound No. 705)Bis[1-phenyl-4-trifluoroisoquinoline-C²,N]-(acetylacetonato)iridium(III) Tris[1-phenyl-4-trifluoroisoquinoline-C²,N]-iridium (III) (ExampleCompound No. 81) Example 43

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 3,5-difluorophenylboronicacid and 1-chloro-5-fluoroisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(3,5-difluorophenyl)-5-fluoroiso-quinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(3,5-difluorophenyl)-5-fluoroisoquinoline-C²,N](acetylacetonato)iridium(III) Tris[1-(3,5-difluorophenyl)-5-fluoroisoquinoline-C²,N]iridium(III) (Example Compound No. 232) Example 44

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-difluorophenylboronicacid and 1-chloro-4-fluoroisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(4-difluorophenyl)-4-fluoroiso-quinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-difluorophenyl)-4-fluoroisoquinoline-C²,N](acetylacetonato)iridium(III) Tris[1-(4-difluorophenyl)-4-fluoroisoquinoline-C²,N]iridium (III)(Example Compound No. 230) Example 45

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-difluorophenylboronicacid and 1-chloro-5-fluoroisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(4-difluorophenyl)-5-fluoroiso-quinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-difluorophenyl)-5-fluoroisoquinoline-C²,N](acetylacetonato)iridium(III) Tris[1-(4-difluorophenyl)-5-fluoroisoquinoline-C²,N]iridium (III)(Example Compound No. 228) Example 46

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-trifluoromethylphenylboronic acid and 1-chloro-4-fluoroisoquinolineinstead of the 4-methylphenylboronic acid and 1-chloroisoquinoline,respectively, in Example 11.

Tetrakis[1-(4-trifluorofluorophenyl)-4-fluoroisoquinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-trifluoromethylphenyl)-4-fluoroisoquinoline-C²,N](acetylacetonato)iridium(III) Tris[1-(4-trifluoromethylphenyl)-4-fluoroisoquinoline-C²,N]iridium(III) (Example Compound No. 256) Example 47

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-fluorophenylboronic acidand 1-chloro-4-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(4-fluorophenyl)-4-trifluoromethyl-quinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-fluorophenyl)-4-trifluoromethylquinoline-C²,N](acetylacetonato)iridium(III) Tris[1-(4-fluorophenyl)-4-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 231) Example 48

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 4-fluorophenylboronic acidand 1-chloro-5-fluoroisoquinoline instead of the 4-methylphenylboronicacid and 1-chloroisoquinoline, respectively, in Example 11.

Tetrakis[1-(4-fluorophenyl)-5-trifluoromethylisoquinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-fluorophenyl)-5-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium(III) Tris[1-(4-fluorophenyl)-5-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 229) Example 49

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-trifluoromethylphenylboronic acid and1-chloro-4-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(4-trifluoromethylphenyl)-4-trifluoromethylisoquinoline-C²,N](μ-dichloro)diiridium(III) (Example Compound No. 691)Bis[1-(4-trifluoromethylphenyl)-4-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium (III)Tris[1-(4-trifluoromethylphenyl)-4-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No 260) Example 50

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-trifluoromethylphenylboronic acid and1-chloro-5-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(4-trifluoromethylphenyl)-5-trifluoromethylisoquinoline-C²,N)(μ-dichloro)diiridium(III)Bis[1-(4-trifluoromethylphenyl)-5-trifluoromethyl-isoquinoline-C²,N](acetylacetonato)iridium(III)Tris[1-(4-trifluoromethylphenyl)-5-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 255) Example 51

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using3,4,5-trifluorophenylboronic acid (made by Lancaster Co.) and1-chloro-4-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(3,4,5-trifluorophenyl)-4-trifluoromethylquinoline-C²,N](μ-dichloro)diiridium (III)Bis[1-(3,4,5-trifluorophenyl)-4-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium(III)Tris[1-(3,4,5-trifluorophenyl)-4-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 253) Example 52

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using3,4,5-trifluorophenylboronic acid (made by Lancaster Co.) and1-chloro-5-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(3,4,5-trifluorophenyl)-5-trifluoromethylisoquinoline-C²,N](P-dichloro)diiridium(III)Bis[1-(3,4,5-trifluorophenyl)-5-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium(III)Tris[1-(3,4,5-trifluorophenyl)-5-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 250) Example 53

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using3,4,5,6-tetrafluorophenylboronic acid and1-chloro-4-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(3,4,5,6-tetrafluorophenyl)-4-trifluoromethylisoquinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(3,4,5,6-trifluorophenyl)-4-trifluoromethylisoquinoline-C²,N](acetylacetonado)iridium(III)Tris[1-(3,4,5,6-tetrafluorophenyl)-4-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 268) Example 54

It is easy to successively synthesize the following compounds in thesane manner as in Example 11 except for using3,4,5,6-tetrafluorophenylboronic acid and1-chloro-5-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(3,4,5,6-tetrafluorophenyl)-5-trifluoromethylisoquinoline-C²,N](μ-dichloro)diiridium(III) (Example Compound No. 690)Bis[1-(3,4,5,6-tetrafluorophenyl)-5-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium(III)Tris[1-(3,4,5,6-tetrafluorophenyl)-5-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 272) Example 55

It is easy to synthesize 1-chloro-3,4,5,6,7,8-hexafluoroisoquinolinealong the following path according to processes described in references:J. Chem. Soc. C, 1966, 2328-2331; J. Chem. Soc. C, 1971, 61-67; J. Org.Chem., 1971, 29. 329-332 and Org, Syn., 1960, 40, 7-10:

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using3,4,5,6-tetrafluorophenylboronic acid and the above-synthesized1-chloro-3,4,5,6,7,8-hexafluoroisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(3,4,5,6-tetrafluorophenyl)-3,4,5,6,7,8-hexafluoroisoquinoline-C²,N](μ-dichloro)diiridium(III) (Example Compound No 709)Bis[1-(3,4,5,6-tetrafluorophenyl)-3,4,5,6,7,8-hexafluoroisoquinoline-C²,N](acetylacetonato)iridium(III) (Example Compound No. 457)Tris[1-(3,4,5,6-tetrafluorophenyl)-3,4,5,6,7,8-hexafluoroisoquinoline-C²,N]iridium(III) (Example Compound No. 454) Example 56

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 3-isopropylphenylboronicacid (made by Lancaster Co.) instead of the 4-methylphenylboronic acidin Example 11

Tetrakis[1-(5-isopropylphenyl)isoquinoline-C²,N](μ-dichloro)iridium(III)Bis[1-(5-isopropylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) Tris[1-(5-isopropylphenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 315) Example 57

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 3-butylphenylboronic acidinstead of the 4-methylphenylboronic acid in Example 11.

Tetrakis[1-(5-butylphenyl)isoquinoline-C²,N](μ-dichloro)iridium (III)(Example Compound No. 725)Bis[1-(5-butylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)Tris[1-(5-butylphenyl)isoquinoline-C²,N]-iridium (III) (Example CompoundNo. 316) Example 58

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 3-octylphenylboronic acid(made by Lancaster Co.) instead of the 4-methylphenylboronic acid inExample 11.

Tetrakis[1-(5-octylphenyl)isoquinoline-C²,N(μ-dichloro)iridium (III)(Example Compound No. 730)Bis[1-(5-octylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)Tris[1-(5-octylphenyl)isoquinoline-C²,N]-iridium (III) (Example CompoundNo. 321) Example 59

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 3-methoxyphenylboronicacid (made by Lancaster Co.) instead of the 4-methylphenylboronic acidin Example 11.

Tetrakis(1-(5-methoxyphenyl)isoquinoline-C²,N(μ-dichloro)iridium (III)Bis[1-(5-methoxyphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)Tris[1-(5-methoxyphenyl)isoquinoline-C²,N]-iridium (III) (ExampleCompound No. 375) Example 61

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-trifluoromethoxyphenylboronic acid (made by Aldrich Co-) and1-chloro-4-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline. respectively, inExample 11.

Tetrakis[1-(4-trifluoromethoxyphenyl)-4-trifluoromethylisoquinoline-C²,N](μ-dichloro)diiridium(III) Bis[1-(4-trifluoromethoxyphenyl)-4-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium (III)Tris[1-(trifluoromethoxyphenyl)-4-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 411) Example 62

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-trifluoromethoxyphenylboronic acid and1-chloro-5-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(4-trifluoromethoxyphenyl)-5-trifluoromethylisoquinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-trifluoromethoxyphenyl)-5-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium(III)Tris[1-(4-trifluoromethoxyphenyl)-5-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 410) Example 63

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-trifluoromethoxyphenylboronic acid and 1-chloro-4-fluoroisoquinolineinstead of the 4-methylphenylboronic acid and 1-chloroisoquinoline,respectively, in Example 11.

Tetrakis[1-(4-trifluoromethoxyphenyl)-4-fluoroiso-quinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-trifluoromethoxyphenyl)-4-fluoroisoquinoline-C²,N](acetylacetonato)iridium(III)Tris[1-(4-trifluoromethoxyphenyl)-4-fluoroisoquinoline-C²,N]iridium(III) (Example Compound No. 409)

Example 64

Bis[1-(4-propylphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium (III)is synthesized in a similar manner as in Example 11 by using1-(4-propylphenyl)isoquinoline of Example 29 and viatetrakis[1-(4-propylphenyl)isoquinoline-C²,N](μ-dichloro)diiridium(III). It is easy to synthesizebis[1-(4-propylphenyl)isoquinoline-C²,N](1-phenylisoquinoline-C²,N)iridium(III) (Example Compound No 283) by reacting the compound with1-phenylisoquinoline of Example 7.

Example 65

Bis[1-phenylisoquinoline-C²,N]-(acetyl-acetonato)iridium (III) issynthesized in a similar manner as in Example 11 by using1-phenylisoquinoline instead of 1-(4-methylphenyl)isoquinoline ofExample 11 and viatetrakis[1-phenylisoquinoline-C²,N](μ-dichloro)diiridium (III). It iseasy to synthesizebis(1-isoquinoline-C²,N)[1-(4-propylphenyl)-isoquinoline-C²,N)Iridium(III) (Example Compound No. 299) by reacting the compound with1-(4-propylphenyl)-isoquinoline of Example 29.

Example 66

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using 1-(4-hexylphenyl)isoquinoline instead ofthe 2-phenylpyridine used in Example 22.

Bis[1-(4-hexylphenyl)isoquinoline-C²,N](1-phenylisoquinoline-C²,N)iridium(III) (Example Compound No. 287).

Example 67

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using 1-phenylisoquinoline and1-(4-hexylphenyl)-isoquinoline instead of the 2-phenylpyridine and1-phenylisoquinoline, respectively, in Example 22.

Bis(1-phenylisoquinoline-C²,N)[1-(4-hexyphenyl)isoquinoline-C²,N]iridium(III) (Example Compound No. 303).

Example 68

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using 1-(4-octylphenyl)isoquinoline instead ofthe 2-phenylpyridine in Example 22.

Bis[1-(4-octylphenyl)isoquinoline-C²,N](1-phenylisoquinoline-C²,N)iridium(III) (Example Compound No. 289).

Example 69

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using 1-phenylisoquinoline and1-(4-octylphenyl)-isoquinoline instead of the 2-phenylpyridine and1-phenylisoquinoline, respectively, in Example 22.

Bis(1-phenylisoquinoline-C²,N)[1-(4-octylphenyl)isoquinoline-C²,N]iridium(III) (Example Compound No. 305).

Example 70 Preparation of Activated Copper Powder

400 g (2.5 mmole) of copper sulfate is dissolved in 2500 ml of hot waterand then cooled, and 219 mg (3.35 mole) of zinc powder is added theretoat the same temperature. After washing with water by decantation,5%-hydrochloric acid is added thereto until hydrogen gas generation isterminated to dissolve the zinc. Copper powder is recovered byfiltration, washed with water and then with methanol and dried to obtain149 g of activated copper powder.

It is easy to synthesize 4-perfluoro-hexylphenylboronic acid by usingthe activated copper powder along the following path:

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-perfluorohexylphenylboronic acid instead of the 4-methylphenylboronicacid in Example 11.

Tetrakis[I (4-perfluorohexylphenyl)isoquinoline-C²,N](μ-dichloro)iridium(III) (Example Compound No. 715)Bis[1-(4-perfluorohexylpnenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) Tris[1-(4-perfluorohexylphenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 475) Example 71

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-perfluorohexylphenylboronic acid and 1-chloro-4-fluoroisoquinolineinstead of the 4-methylphenylboronic acid and 1-chloroisoquinoline,respectively, in Example 11.

Tetrakis[1-(4-perfluorohexylphenyl)-4-fluoroisoquinoline-C²,N](μ-dichloro),diiridium(III)Bis[1-(4-perfluorohexylphenyl)-4-fluoroisoquinoline-C²,N](acetylacetonato)iridium(III) Tris[1-(4-perfluorohexylphenyl) 4-fluoroisoquinoline-C²,N]iridium(III) (Example Compound No. 478) Example 72

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-perfluorohexylphenylboronic acid and1-chloro-4-trifluoromethylisoquinoline instead of the4-methylphenylboronic acid and 1-chloroisoquinoline, respectively, inExample 11.

Tetrakis[1-(4-perfluorohexylphenyl)-4-trifluoromethylisoquinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-perfluorohexylphenyl)-4-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium(III) Tris[1-(4-perfluorohexylphenyl)-4-trifluoromethylisoquinoline-C²,N]iridium (III) (Example Compound No. 477) Example 73

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-perfluorohexylphenylboronic acid and 1-chloro-5-fluoroisoquinolineinstead of the 4-methylphenylboronic acid and 1-chloroisoquinoline,respectively, in Example 11.

Tetrakis[1-(4-perfluorohexylphenyl)-5-trifluoromethylisoquinoline-C²,N](μ-dichloro)diiridium(III)Bis[1-(4-perfluorohexylphenyl)-5-trifluoromethylisoquinoline-C²,N](acetylacetonato)iridium(III)Tris[1-(4-perfluorohexylphenyl)-5-trifluoromethylisoquinoline-C²,N]iridium(III) (Example Compound No. 476) Example 74

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using 1-(4-perfluorohexylphenyl)isoquinolineinstead of the 2-phenylpyridine in Example 22.

Bis[1-(4-perfluorohexylphenyl)isoquinoline-C²,N](1-phenylisoquinoline-C²,N)iridium(III) (Example Compound No. 479).

Example 75

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using 1-phenylisoquinoline and1-(4-perfluorohexylphenyl)isoquinoline instead of the 2-phenylpyridineand 1-phenylisoquinoline, respectively, in Example 22.

Bis1-phenylisoquinoline-C²,N)[1-(4-perfluorohexylphenyl)isoquinoline-C²,N]iridium(III) (Example Compound No. 480).

Example 76

It is easy to synthesize 4-(1H,1H,2H,2H-perfluoropentyloxy)phenylboronicacid along the following the path:

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using4-(1H,1H,2H,2H-perfluoropentyloxy)-phenylboronic acid instead of the4-methylphenylboronic acid in Example 11.

Tetrakis{1-[4-(1H,1H,2H,2H-perfluoropentyloxy)-phenyl]isoquinoline-C²,N}(μ-dichloro)iridium(III)Bis{1-[4-(1H,1H,2H,2H-perfluoropentyloxy)phenyl]-isoquinoline-C²,N}-(acetylacetonato)iridium(III)Tris{1-[4-(1H,1H,2H,2H-perfluoropentyloxyethylphenyl]isoquinoline-C²,N}-iridium(III) (Example Compound No. 469) Example 77

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using1-[4-(1H,1H,2H,2H-perfluoropentyloxy)-isoquinoline instead of the2-phenylpyridine in Example 22.

Bis{1-[4-(1H,1H,2H,2H]-perfluoropentyloxy)-phenyl]isoquinoline-C²,N}(1-phenylisoquinoline-C²,N)-iridium(III) (Example Compound No. 470).

Example 78

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using 1-phenylisoquinoline and1-[4-(1H,1H,2H,2H-perfluoropentyloxy)phenyl]isoquinoline instead of the2-phenylpyridine and 1-phenylisoquinoline, respectively, in Example 22.

Bis(1-phenylisoquinoline-C²,N){1-[4-(1H,1H,2H,2H-perfluoropentyloxy)phenyl]isoquinoline-C²,N}iridium(III) (Example Compound No. 471).

Example 79

It is easy to synthesize 4-(1H,1H-perfluoro-heptyloxy)phenylboronic acidalong the following path:

It is easy to successively synthesize the following compounds in thesame manner as in example 11 except for using4-(1H,1H-perfluoroheptyloxy)-phenylboronic acid instead of the4-methylphenyl-boronic acid in Example 11.

Tetrakis{1-[4-(1H,1H-perfluoroheptyloxy)phenyl]-isoquinoline-C²,N}(μ-dichloro)iridium(III) Bis{1-[4-(1H,1H-perfluoroheptyloxy)phenyl]-isoquinoline-C²,N}-(acetylacetonato)iridium(III)Tris{1-[4-(1H,1H-perfluoroheptyloxy)phenyl]-isoquinoline-C²,N}-iridium(III) (Example Compound No. 481) Example 80

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using1-[4-(1H,1H-perfluoroheptyloxy)phenyl]-isoquinoline instead of the2-phenylpyridine in Example 22.

Bis{1-[4-(1H,1H-perfluoroheptyloxy)phenyl]-isoquinoline-C²,N}(1-phenylisoquinoline-C²,N)iridium(III) (Example Compound No. 483).

Example 81

It is easy to synthesize the following compound in a similar manner asin Example 22 except for using 1-phenylisoquinoline and1-[4-(1H,1H-perfluoroheptyloxy)phenyl]isoquinoline instead of the2-phenylpyridine and 1-phenylisoquinoline, respectively, in Example 22.

Bis(1-phenylisoquinoline-C²,N){1-[4-(1H,1H-perfluoroheptyloxy)phenyl]isoquinoline-C²,N}iridium(III) (Example Compound No. 484).

Example 82

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using phenylboronic acid and1-chloro-4-hexylisoquinoline instead of the 4-methylphenylboronic acidand 1-chloroisoquinoline, respectively, in Example 11.

Tetrakis[1-phenyl-4-hexylisoquinoline-C²,N](μ-dichloro)diiridium (III)Bis[1-phenyl-4-hexylisoquinoline-C²,N](acetyl-acetonato)iridium (III)Tris[1-phenyl-4-hexylisoquinoline-C²,N]iridium (111) (Example CompoundNo. 156) Example 83

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using phenylboronic acid and1-chloro-5-fluoroisoquinoline instead of the 4-methylphenylboronic acidand 1-chloroisoquinoline, respectively, in Example 11.

Tetrakis(1-phenyl-5-octylisoquinoline-C²,N)(μ-dichloro)diiridium (III)Bis(1-phenyl-5-octylisoquinoline-C²,N)(acetyl-acetonato)iridium (III)Tris(1-phenyl-5-octylisoquinoline-C²,N)iridium (III) (Example CompoundNo. 220) Example 84

It is easy to successively synthesize the following compounds in thesame manner as in Example 11 except for using 3-heptyloxyphenylboronicacid (made by Lancaster Co.) instead of the 4-methylphenylboronic acidin Example 11.

Tetrakis[1-(5-heptyloxyphenyl)isoquinoline-C²,N](μ-dichloro)iridium(III)Bis[1-(5-heptyloxyphenyl)isoquinoline-C²,N]-(acetylacetonato)iridium(III) Tris[1-(5-heptyloxyphenyl)isoquinoline-C²,N]-iridium (III)(Example Compound No. 270) Example 85

It is easy to synthesize 1-chloro-7-azaisoquinoline by using2,6-dihydroxy-4-methyl-3-pyridylcarbonitrile (made by Aldrich Co.,catalog 37, 947-6) along the following path described in U.S. Pat. No.4,859,671:

It is easy to synthesize 1-phenyl-7-azaisoquinoline by using1-chloro-7-azaisoquinoline instead of the 1-chloroisoquinoline inExample 7, and successively synthesizetetrakis(1-phenyl-7-azaisoquinoline-C²,N)(μ-dichloro)diiridium (III) andbis(1-phenyl-7-azaisoquinoline-C²,N)(acetylacetonato)-iridium (III) toobtain tris(1-phenyl-7-azaiso-quinoline-C²,N)iridium (III) (ExampleCompound No. 783) in-a similar manner as in Example 11.

Example 86

It is easy to synthesize 1-hydroxy-5-azaisoquinoline by using3-methyl-picolinonitrile (made by Aldrich Co-, catalog 51, 273-7) alongthe following path described in U.S. Pat. No. 4,176,183 and synthesize1-chloro-5-azaisoquinoline in a similar manner as in Example 85.

It is easy to synthesize 1-phenyl-5-azaisoquinoline by using1-chloro-5-azaisoquinoline instead of the 1-chloroisoquinoline inExample 7, and successively synthesizetetrakis(1-phenyl-5-azaisoquinoline-C²,N)(μ-dichloro)diiridium (III)(Example Compound No. 763) andbis(1-phenyl-5-azaisoquinoline-C²,N)(acetylacetonato)iridium (III) toobtain tris(1-phenyl-5-azaisoquinoline-C²,N)iridium (III) (ExampleCompound No. 640) in a similar manner as in Example 11.

Examples 87-95

Devices having a similar structure as in Example 1 were prepared andevaluated. Details of device structures, layer thicknesses andevaluation results are shown in Table 25. TABLE 25 Device structure*current luminance current efficiency power efficiency Example No. H.T.L.luminescence layer E.D.P.L. E.T.L. mA/cm2 cd/m2 cd/A lm/W 87 αNPD CBP:Compound No. 413(7%) BCP Alq 3 10 volts 10 volts 100 cd/m2 300 cd/m2 100cd/m2 300 cd/m2 40 nm 40 nm 10 nm 20 nm 114 800 1    0.86 0.4  0.3 88αNPD CBP: Compound No. 432(7%) BCP Alq 3 10 V 10 V 100 cd 300 cd 100 cd300 cd 40 40 10 20 26 1248  5.9 5.5 2.8  2.1 89 αNPD CBP: Compound No.408(5%) BCP Alq 3 10 V 10 V 100 cd 300 cd 100 cd 300 cd 40 40 10 60 9480 6.6 5.6 2.4 1.8 90 αNPD CBP: Compound No. 433(5%) BCP Alq 3 10 V 10V 100 cd 300 cd 100 cd 300 cd 40 40 10 60 12 700  6.69 6.4 2.93  2.32 91αNPD CBP: Compound No. 433(7%) BCP Alq 3 10 V 100 cd 300 cd 100 cd 300cd 40 40 10 60 12.2 876 8.6 7.8 3.82 2.9 92 αNPD CBP: Compound No.433(9%) BCP Alq 3 10 V 100 cd 300 cd 100 cd 300 cd 40 40 10 60 18 1180 7.5 7.2 3.86 2.9 93 αNPD CBP: Compound No. 517(7%) BCP Alq 3 10 V 100 cd300 cd 100 cd 300 cd 40 40 10 60 3.3 185  5.75  5.42 1.95  1.54 94 αNPDCBP: Compound No. 516(7%) Balq Alq 3 10 V 100 cd 300 cd 100 cd 300 cd 4040 10 60 12.5 611  5.85  5.25 2.42  1.80 95 αNPD CBP: Ir Compound No.412(7%) Balq Alq 3 10 V 100 cd 300 cd 100 cd 300 cd 40 40 10 60 15 7785.3 5.4 2.2  1.9*H.T.L. = hole-transporting layer E.D.P.L. = excitondiffusion-prevention layer E.T.L. = electron-transporting layer

Balq used in the exciton diffusion-prevention layer used in Examples 94and 95 has a structure shown below.

INDUSTRIAL APPLICABILITY

As described above, the luminescence device of the present inventionusing, as a luminescence center material, a metal coordination compoundhaving a partial structure of the above formula (1) and particularlyrepresented by the above formula (3) is an excellent device which notonly allows high-efficiency luminescence but also retains a highluminance for a long period and allows luminescence of longerwavelength. Further, the luminescence device of the present inventionshows excellent performances as a red display device.

1. A metal coordination compound represented by a structure selectedfrom the group consisting of structures (A)-(D):

wherein L is a ligand represented by a following formula (2):

wherein R₁ to R₁₀ independently denote H or a substituent other than F,and wherein L2 is a ligand different from L and is selected from thegroup consisting of formulas (4)-(6):

wherein N and C are nitrogen and carbon atoms, respectively; wherein A′is a substituted or unsubstituted cyclic group, which is bonded to Irvia the carbon atom; wherein B′ and B″ are each a substituted orunsubstituted cyclic group, which is bonded to Ir via the nitrogen atom,with a proviso that the cyclic group A′ and the cyclic group B′ arecoordination-bonded to each other; and wherein each substituent of thecyclic group is independently selected from: a halogen atom, a cyanogroup, a nitro group, a di-substituted amino group, of whichsubstituents are independently a phenyl group or a naphthyl group eachoptionally substituted by a halogen atom, a methyl group or atrifluoromethyl group, or a linear or branched alkyl group having 1 to 8carbon atoms and including a hydrogen atom optionally replaced with afluorine atom, or a trialkylsilyl group in which the alkyl groups areindependently a linear or branched alkyl group having 1 to 8 carbonatoms, or a linear or branched alkyl group having 1 to 20 carbon atoms,in which the alkyl group optionally includes one methylene group or twoor more non-neighboring methylene groups that can be replaced with —O—,—S—, —C(O)—, —C(O)—O—, —O—C(O)—, —CH═CH—, —C≡C—, or a divalent aromaticgroup optionally having a substituent, which is a halogen atom, a cyanogroup, a nitro group, a trialkylsilyl group, in which the alkyl groupsare independently a linear or branched alkyl group, a linear or branchedalkyl group having 1 to 20 carbon atoms, in which the alkyl groupoptionally includes one methylene group or two or more non-neighboringmethylene groups that can be replaced with —O—, —S—, —C(O)—, —C(O)—O—,—O—C(O)—, —CH═CH—, —C≡C—, and the alkyl group optionally includes ahydrogen atom that can be optionally replaced with a fluorine atom, andthe alkyl group includes a hydrogen atom that can be optionally replacedwith a fluorine atom, with a proviso that an adjacent pair ofsubstituents can be bonded to form a cyclic structure; and wherein E, Gand J are independently a linear or branched alkyl group having 1 to 20carbon atoms and the alkyl group can include a hydrogen atom that can beoptionally replaced with a fluorine atom and the alkyl group optionallyincludes one methylene group or two or more non-neighboring methylenegroups that can be replaced with —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)—,—CH═CH—, —C≡C—, or a divalent aromatic group capable of having asubstituent, which is a halogen atom, a cyano atom, a nitrogen atom, atrialkylsilyl group in which the alkyl groups are independently a linearor branched alkyl group, or a linear or branched alkyl group having 1 to20 carbon atoms in which the alkyl group optionally includes onemethylene group or two or more non-neighboring methylene groups that canbe replaced with —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)—, —CH═CH—, —C≡C—,and the alkyl group includes a hydrogen atom that can be optionallyreplaced with a fluorine atom, with a proviso that an adjacent pair ofsubstituents can be bonded to form a cyclic structure, or adi-substituted amino group in which substituents are independently aphenyl group or a naphthyl group each capable of having a substituent,which is selected from the group consisting of halogen atom, a methylgroup and a trifluoromethyl group, or a linear or branched alkyl grouphaving 1 to 8 carbon atoms and including a hydrogen atom optionallyreplaced with a fluorine atom, and wherein J is optionally a hydrogenatom;

wherein L is a ligand represented by the formula (2), where R₁ to R₁₀independently denote H or a substituent other than F, with a provisothat at least one of R₁ to R₁₀ is not H, and wherein L2 is a liganddifferent from L and is represented by the formula (4); (C) the formula(3), wherein L is a substituted or unsubstituted ligand represented bythe formula (2), and wherein L2 is represented by the formula (5) or(6); and (D) the formula (3), wherein L is an unsubstituted ligandrepresented by the formula (2), and wherein L2 is represented by theformula (4), with a proviso that it is not a phenylpyridine or aphenylisoquinoline ligand.
 2. The metal coordination compound accordingto claim 1, having the structure (A).
 3. The metal coordination compoundaccording to claim 1, having the structure (B).
 4. The metalcoordination compound according to claim 1, having the structure (C). 5.The metal coordination compound according to claim 1, having thestructure (D).
 6. An organic luminescence device comprising: an anodeand a cathode; and an organic layer disposed between the anode and thecathode, wherein the organic layer comprises a metal coordinationcompound according to claim
 2. 7. A picture display apparatuscomprising: an organic luminescence device according to claim 6; andmeans for supplying an electrical signal to the organic luminescencedevice.
 8. An organic luminescence device comprising: an anode and acathode; and an organic layer disposed between the anode and thecathode, wherein the organic layer comprises a metal coordinationcompound according to claim
 3. 9. A picture display apparatuscomprising: an organic luminescence device according to claim 8; andmeans for supplying an electrical signal to the organic luminescencedevice.
 10. An organic luminescence device comprising: an anode and acathode; and an organic layer disposed between the anode and thecathode, wherein the organic layer comprises a metal coordinationcompound according to claim
 4. 11. A picture display apparatuscomprising: an organic luminescence device according to claim 10; andmeans for supplying an electrical signal to the organic luminescencedevice.
 12. An organic luminescence device comprising: an anode and acathode; and an organic layer disposed between the anode and thecathode, wherein the organic layer comprises a metal coordinationcompound according to claim
 5. 13. A picture display apparatuscomprising: an organic luminescence device according to claim 12; andmeans for supplying an electrical signal to the organic luminescencedevice.